U.S. patent application number 11/929212 was filed with the patent office on 2009-01-08 for high metathesis activity ruthenium and osmium metal carbene complexes.
This patent application is currently assigned to CALIFORNIA INSTITUTE OF TECHNOLOGY. Invention is credited to Robert H. GRUBBS, Sonbinh T. NGUYEN, Peter SCHWAB.
Application Number | 20090012254 11/929212 |
Document ID | / |
Family ID | 27357023 |
Filed Date | 2009-01-08 |
United States Patent
Application |
20090012254 |
Kind Code |
A1 |
GRUBBS; Robert H. ; et
al. |
January 8, 2009 |
HIGH METATHESIS ACTIVITY RUTHENIUM AND OSMIUM METAL CARBENE
COMPLEXES
Abstract
Ruthenium and osmium carbene compounds that are stable in the
presence of a variety of functional groups and can be used to
catalyze olefin metathesis reactions on unstrained cyclic and
acyclic olefins are disclosed. Also disclosed are methods of making
the carbene compounds. The carbene compounds are of the formula
##STR00001## where M is Os or Ru; R.sup.1 is hydrogen; R is
selected from the group consisting of hydrogen, substituted or
unsubstituted alkyl, and substituted or unsubstituted aryl; X and
X.sup.1 are independently selected from any anionic ligand; and L
and L.sup.1 are independently selected from any neutral electron
donor. The ruthenium and osmium carbene compounds of the present
invention may be synthesized using diazo compounds, by neutral
electron donor ligand exchange, by cross metathesis, using
acetylene, using cumulated olefins, and in a one-pot method using
diazo compounds and neutral electron donors. The ruthenium and
osmium carbene compounds of the present invention may be used to
catalyze olefin metathesis reactions including, but not limited to,
ROMP, RCM, depolymerization of unsaturated polymers, synthesis of
telechelic polymers, and olefin synthesis.
Inventors: |
GRUBBS; Robert H.; (S.
Pasadena, CA) ; SCHWAB; Peter; (East Hanover, NJ)
; NGUYEN; Sonbinh T.; (Evanston, IL) |
Correspondence
Address: |
NIXON PEABODY, LLP
401 9TH STREET, NW, SUITE 900
WASHINGTON
DC
20004-2128
US
|
Assignee: |
CALIFORNIA INSTITUTE OF
TECHNOLOGY
Pasadena
CA
|
Family ID: |
27357023 |
Appl. No.: |
11/929212 |
Filed: |
October 30, 2007 |
Related U.S. Patent Documents
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11472137 |
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7288666 |
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11929212 |
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10968361 |
Oct 18, 2004 |
7102047 |
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11472137 |
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10325998 |
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6806325 |
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10968361 |
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09746146 |
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6515084 |
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10325998 |
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09399963 |
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6211391 |
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09746146 |
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09007498 |
Jan 15, 1998 |
6111121 |
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09399963 |
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08693789 |
Jul 31, 1996 |
5831108 |
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09007498 |
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60001862 |
Aug 3, 1995 |
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60003973 |
Sep 19, 1995 |
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Current U.S.
Class: |
528/9 |
Current CPC
Class: |
C08F 32/00 20130101;
B01J 31/2404 20130101; B01J 31/2265 20130101; C08G 61/08 20130101;
B01J 31/18 20130101; B01J 2231/543 20130101; B01J 2231/14 20130101;
C08F 4/80 20130101; B01J 31/24 20130101; B01J 2531/825 20130101;
C07F 15/0046 20130101; C07F 15/002 20130101; B01J 2531/821
20130101 |
Class at
Publication: |
528/9 |
International
Class: |
C08G 79/00 20060101
C08G079/00 |
Goverment Interests
[0002] The U.S. Government has certain rights in this invention
pursuant to Grant No. CHE-8922072 awarded by the National Science
Foundation.
Claims
1-33. (canceled)
34. A process for synthesizing telechelic polymers by metathesis
polymerization, comprising contacting a cyclic olefin with a
compound of the formula: ##STR00024## in the presence of an
.alpha.,.omega.-difunctional olefin, wherein: M is selected from
the group consisting of Os and Ru; R.sup.1 is hydrogen; R is
selected from the group consisting of hydrogen, substituted or
unsubstituted alkyl, and substituted or unsubstituted aryl; X and
X.sup.1 are independently selected from any anionic ligand; L and
L.sup.1 is selected from any neutral electron donor.
35. A process for synthesizing olefins by metathesis, comprising
contacting an acyclic olefin with a compound of the formula:
##STR00025## wherein: M is selected from the group consisting of Os
and Ru; R.sup.1 is hydrogen; R is selected from the group
consisting of hydrogen, substituted or unsubstituted alkyl, and
substituted or unsubstituted aryl; X and X.sup.1 are independently
selected from any anionic ligand; L and L.sup.1 are selected from
any neutral electron donor.
36. A process for synthesizing olefins by cross metathesis,
comprising contacting a first acyclic olefin with a compound of the
formula: ##STR00026## in the presence of a second acyclic olefin,
wherein: M is selected from the group consisting of Os and Ru;
R.sup.1 is hydrogen; R is selected from the group consisting of
hydrogen, substituted or unsubstituted alkyl, and substituted or
unsubstituted aryl; X and X.sup.1 are independently selected from
any anionic ligand; L and L.sup.1 are selected from any neutral
electron donor.
37-42. (canceled)
Description
[0001] This application claims the benefit of U.S. Provisional
application No. 60/001,862, filed Aug. 3, 1995, and U.S.
Provisional application No. 60/003,973, filed Sep. 19, 1995, both
of which are incorporated herein by reference.
BACKGROUND
[0003] This invention relates to highly active and stable ruthenium
and osmium metal carbene complex compounds, their synthesis and use
as catalysts for olefin metathesis reactions.
[0004] Transition-metal catalyzed C--C bond formation via olefin
metathesis is of considerable interest and synthetic utility.
Initial studies in this area were based on catalytically active
mixtures consisting of transition-metal chlorides, oxides or
oxychlorides, cocatalysts such as EtAlCl.sub.2 or R.sub.4Sn, and
promoters including O.sub.2, EtOH or PhOH. For example,
WCl.sub.6/EtAlCl.sub.2/EtOH 1:4:1. These systems catalyze olefin
metathesis reactions, however their catalytic centers are
ill-defined and systematic control of their catalytic activity is
not possible.
[0005] Recent efforts have been directed towards the development of
well-defined metathesis active catalysts based on transition metal
complexes. The results of research efforts during the past two
decades have enabled an in-depth understanding of the olefin
metathesis reaction as catalyzed by early transition metal
complexes. In contrast, the nature of the intermediates and the
reaction mechanism for Group VIII transition metal catalysts have
remained elusive. In particular, the oxidation states and ligation
of the ruthenium and osmium metathesis intermediates are not
known.
[0006] Group VIII transition metal olefin metathesis catalysts,
specifically ruthenium and osmium carbene complexes, have been
described in U.S. Pat. Nos. 5,312,940 and 5,342,909 and U.S. patent
applications Ser. Nos. 08/282,826 and 08/282,827, all of which are
incorporated herein by reference. The ruthenium and osmium carbene
complexes disclosed in these patents and applications are of the
general formula
##STR00002##
where M is ruthenium or osmium, X and X' are anionic ligands, and L
and L' are neutral electron donors.
[0007] U.S. Pat. Nos. 5,312,940 and 5,342,909 disclose specific
vinyl alkylidene ruthenium and osmium complexes and their use in
catalyzing the ring opening metathesis polymerization ("ROMP") of
strained olefins. In all of the specific alkylidene complexes
disclosed in these patents, R.sup.1 is hydrogen and R is either a
substituted or unsubstituted vinyl group. For example, a preferred
vinyl alkylidene complex disclosed in these patents is
##STR00003##
where Ph is phenyl.
[0008] U.S. patent applications Ser. Nos. 08/282,826 and 08/282,827
disclose specific vinyl alkylidene ruthenium and osmium complexes
and their use in catalyzing a variety of metathesis reactions. The
catalysts disclosed in these applications have specific neutral
electron donor ligands L and L.sup.1; namely, phosphines in which
at least one substituent is a secondary-alkyl or cycloalkyl group.
As in the above U.S. patents, in all of the specific alkylidene
complexes disclosed in the patent applications, R' is hydrogen and
R is either a substituted or unsubstituted vinyl group. For
example, a preferred vinyl alkylidene complex disclosed in these
patent applications is
##STR00004##
where Cy is cyclohexyl.
[0009] Although the vinyl alkylidene complexes disclosed in the
above patents and patent applications exhibit high metathesis
activity and remarkable stability towards functional groups there
are at least two drawbacks to these complexes as metathesis
catalysts. First, the preparation of the vinyl alkylidene complexes
requires a multi-step synthesis; and second, the vinyl alkylidene
complexes have relatively low initiation rates. Both of these
aspects of the vinyl alkylidene complexes are undesirable for their
use as metathesis catalysts. The multi-step synthesis may be time
consuming and expensive and may result in lower product yields. The
low initiation rate may result in ROMP polymers with a broad
molecular weight distribution and prolonged reaction times in ring
closing metathesis ("RCM") reactions.
[0010] For the reasons discussed above, there is a need for
well-defined metathesis active catalysts that have the following
characteristics: first, they are stable in the presence of a wide
variety of functional groups; second, they can catalyze a variety
of metathesis reactions including the metathesis of acyclic and
unstrained cyclic olefins; third, they have a high initiation rate;
and fourth, they are easily prepared. Furthermore, there is a need
for olefin metathesis catalysts that can catalyze the ROMP of
strained and unstrained cyclic olefins to yield polymers of very
low polydispersity (i.e., POI=1.0) and that can catalyze the RCM of
acyclic dienes with short reaction times.
SUMMARY
[0011] The present invention meets the above needs and provides
well-defined ruthenium and osmium carbene compounds that are stable
in the presence of a variety of functional groups and can be used
to catalyze olefin metathesis reactions on unstrained cyclic and
acyclic olefins. The compounds of the present invention are highly
active in metathesis reactions and have high initiation rates.
[0012] In one embodiment of the present invention, the ruthenium
and osmium carbene compounds have the formula
##STR00005##
where M may be Os or Ru; R.sup.1 is hydrogen; X and X.sup.1 may be
different or the same and are any anionic ligand; L and L.sup.1 may
be different or the same and are any neutral electron donor; and R
may be hydrogen, substituted or unsubstituted alkyl, or substituted
or unsubstituted aryl.
[0013] The ruthenium and osmium carbene complexes of the present
invention are stable in the presence of a variety of functional
groups. A consequence of this is that the alkyl and aryl R group
may contain one or more functional groups including alcohol, thiol,
ketone, aldehyde, ester, ether, amine, imine, amide, nitro,
carboxylic acid, disulfide, carbonate, isocyanate, carbodiimide,
carboalkoxy, and halogen groups.
[0014] R is preferably hydrogen, C.sub.1-C.sub.20 alkyl, or aryl.
The C.sub.1-C.sub.20 alkyl may optionally be substituted with one
or more aryl, halide, hydroxy, C.sub.1-C.sub.20 alkoxy, or
C.sub.2-C.sub.20 alkoxycarbonyl groups. The aryl may optionally be
substituted with one or more C.sub.1-C.sub.20 alkyl, aryl,
hydroxyl, C.sub.1-C.sub.5 alkoxy, amino, nitro, or halide
groups.
[0015] L and L.sup.1 are preferably phosphines of the formula
PR.sup.3R.sup.4R.sup.5, where R.sup.3 is a secondary alkyl or
cycloalkyl, and R.sub.4 and R.sub.5 are aryl, C.sub.1-C.sub.10
primary alkyl, secondary alkyl, or cycloalkyl. R.sup.4 and R.sup.5
may be the same or different.
[0016] L and L.sup.1 are are most preferably the same and
--P(cyclohexyl).sup.3, --P(cyclopentyl).sup.3, or
--P(isopropyl).sup.3.
[0017] X and X.sup.1 are most preferably the same and are
chlorine.
[0018] In another embodiment of the present invention, the
ruthenium and osmium carbene compounds have the formula
##STR00006##
where M may be Os or Ru; X and X.sup.1 may be different or the same
and are any anionic ligand; L and L.sup.1 may be different or the
same and are any neutral electron donor; and R.sup.9 and R.sup.10
may be different or the same and may be hydrogen, substituted or
unsubstituted alkyl, or substituted or unsubstituted aryl. The
R.sup.9 and R.sup.10 groups may optionally include one or more of
the following functional groups: alcohol, thiol, ketone, aldehyde,
ester, ether, amine, imine, amide, nitro, carboxylic acid,
disulfide, carbonate, isocyanate, carbodiimide, carboalkoxy, and
halogen groups
[0019] The ruthenium and osmium carbene compounds of the present
invention may be used to catalyze olefin metathesis reactions
including, but not limited to, ROMP, RCM, depolymerization of
unsaturated polymers, synthesis of telechelic polymers, and olefin
synthesis.
[0020] In the ROMP reaction, a compound according to the present
invention is contacted with a cyclic olefin to yield a ROMP polymer
product. In the RCM reaction, a compound according to the present
invention is contacted with a diene to yield a ring-closed product.
In the depolymerization reaction, a compound according to the
present invention is contacted with an unsaturated polymer in the
presence of an acyclic olefin to yield a depolymerized product. In
the synthesis of telechelic polymers, a compound according to the
present invention is contacted with a cyclic olefin in the presence
of an .alpha.,.omega.-difunctional olefin to yield a telechelic
polymer. In the olefin synthesis reaction, a compound according to
the present invention is contacted with one or two acyclic olefins
to yield self-metathesis or cross-metathesis olefin products.
[0021] Since the ruthenium and osmium carbene compounds of the
present invention are stable in the presence of a variety of
functional groups, the olefins involved in the above reactions may
optionally be substituted with one or more functional groups
including alcohol thiol, ketone, aldehyde, ester, ether, amine,
imine, amide, nitro, carboxylic acid, disulfide, carbonate,
isocyanate, carbodiimide, carboalkoxy, and halogen groups.
[0022] The above reactions may be carried out in aqueous, protic,
or organic solvents or mixtures of such solvents. The reactions may
also be carried out in the absence of a solvent. The reactants may
be in the gas phase or liquid phase.
[0023] The ruthenium and osmium carbene compounds of the present
invention may be synthesized using diazo compounds by neutral
electron donor ligand exchange, by cross metathesis, using
acetylene, using cumulated olefins, and in a one-pot method using
diazo compounds and neutral electron donors.
BRIEF DESCRIPTION OF THE DRAWINGS
[0024] The invention will be better understood by reference to the
appended figures wherein:
[0025] FIGS. 1A and 1B are representative kinetic plots for acyclic
metathesis of 1-hexene with RuCl.sub.2(.dbd.CHPh)(PCy.sub.3).sub.2
(complex 10) at 0.degree. C.; and
[0026] FIG. 2 is an ORTEP plot of
RuCl.sub.2(.dbd.CH-p-C.sub.6H.sub.4Cl)(PCy.sub.3).sub.2 (complex
15).
DETAILED DESCRIPTION OF THE INVENTION
[0027] The abbreviations Me, Ph, .sup.iPr or i-Pr, Cy, Cp, n-Bu,
and THF refer to methyl, phenyl, isopropyl, cyclohexyl,
cyclopentyl, n-butyl, and tetrahydrofuran, respectively.
[0028] While previous investigations have explored the influence of
the neutral electron donor and anionic ligands (i.e. L, L.sup.1, X,
and X.sup.1) on the stability and utility of the ruthenium and
osmium carbene complexes, the effect of variation of the alkylidene
moieties (R and R.sup.1) had not been studied. By studying the
effect of these substituents, it has been discovered that ruthenium
and osmium complexes containing the specific alkylidene moieties of
the present invention have unexpectedly high initiation rates
compared to the vinyl alkylidene complexes previously described.
Quantitative data is included below that demonstrates that the
initiation rates of the complexes of the present invention are
approximately a thousand times higher than the initiation rates of
the corresponding vinyl alkylidene complexes. In addition to having
unexpectedly high initiation rates, the complexes of the present
invention are stable in the presence of a variety of functional
groups and have high metathesis activity allowing them to catalyze
a variety of metathesis reactions including metathesis reactions
involving acyclic and unstrained cyclic olefins.
[0029] The compounds of the present invention are ruthenium and
osmium alkylidene complexes of the general formula
##STR00007##
where R.sup.1 is hydrogen and R is selected from the specific group
described below. Generally X and X.sup.1 can be any anionic ligand
and L and L.sup.1 can be any neutral electron donor. Specific
embodiments of X, X.sup.1, L, and L.sup.1 are described in detail
in U.S. Pat. Nos. 5,312,940 and 5,342,909 and U.S. patent
applications Ser. Nos. 08/282,826 and 08/282,827.
[0030] R may be hydrogen, substituted or unsubstituted alkyl, or
substituted or unsubstituted aryl. The ruthenium and osmium carbene
complexes of the present invention are stable in the presence of a
variety of functional groups. A consequence of this is that the
alkyl and aryl R groups may contain a variety of functional groups
including alcohol, thiol, ketone, aldehyde, ester, ether, amine,
imine, amide, nitro, carboxylic acid, disulfide, carbonate,
isocyanate, carbodiimide, carboalkoxy, and halogen groups.
[0031] In a preferred embodiment R is hydrogen, C.sub.1-C.sub.20
alkyl, or aryl. The C.sub.1-C.sub.20 alkyl may optionally be
substituted with one or more aryl, halide, hydroxy,
C.sub.1-C.sub.20 alkoxy, or C.sub.2-C.sub.20 alkoxycarbonyl groups.
The aryl may optionally be substituted with one or more
C.sub.1-C.sub.20 alkyl, aryl, hydroxyl, C.sub.1-C.sub.5 alkoxy,
amino, nitro, or halide groups. In a more preferred embodiment, R
is hydrogen, C.sub.1-C.sub.4 alkyl, phenyl, C.sub.1-C.sub.4 alkyl
substituted with one or more groups selected from the group
consisting of halide, hydroxy, and C.sub.2-C.sub.6 alkoxycarbonyl,
or phenyl substituted with one or more groups selected from the
group consisting of C.sub.1-C.sub.5 alkyl, C.sub.1-C.sub.5 alkoxy,
amino, nitro, and halide.
[0032] In a more preferred embodiment R may be hydrogen, methyl,
ethyl, n-butyl, iso-propyl, --CH.sub.2Cl,
--CH.sub.2CH.sub.2CH.sub.2OH, --CH.sub.2OAc, phenyl. The phenyl may
optionally be substituted with a chloride, bromide, iodide,
fluoride, --NO.sub.2, --NMe.sub.2, methoxy, or methyl group. In a
more preferred embodiment, the phenyl is para-substituted.
[0033] In a most preferred embodiment R is phenyl.
[0034] Preferred complexes of the present invention include
##STR00008##
where R is cyclohexyl, cyclopentyl, iso-propyl, or phenyl.
[0035] The most preferred complex of the present invention is
##STR00009##
[0036] The ruthenium and osmium alkylidene complexes of the present
invention may be synthesized by a variety of different methods
including those taught in P. Schwab et al. Angew. Chem. Int. Ed.
Engl. 34, 2039-2041 (1995), and P. Schwab et al. J. Am. Chem. Soc.
118, 100-110 (1996), both of which are incorporated herein by
reference.
[0037] The ruthenium and osmium complexes of the present invention
may be synthesized by alkylidene transfer from diazoalkanes. This
synthetic method may generally be written as
##STR00010##
where M, X, X.sup.1, L, L.sup.1, R and R.sup.1 are as described
above; m and n are independently 0-3 such that m+n=3; and p is a
positive integer. In the diazo synthesis, a compound of the formula
(XX.sup.1ML.sub.n L.sup.1.sub.m)p is contacted with a diazo
compound of the formula RC(N.sub.2)R.sup.1 to yield an alkylidene
according to the present invention.
[0038] The ruthenium and osmium complexes of the present invention
may also be synthesized by neutral electron donor ligand exchange
as disclosed in U.S. Pat. Nos. 5,312,940 and 5,342,909 and U.S.
patent applications Ser. Nos. 08/282,826 and 08/282,827.
[0039] The ruthenium and osmium complexes of the present invention
may also be synthesized by cross metathesis. This method may
generally be written as
##STR00011##
where R.sup.11 and R.sup.12 may be the same or different and may be
hydrogen, substituted or unsubstituted alkyl, or substituted or
unsubstituted aryl.
[0040] The ruthenium and osmium complexes of the present invention
may also be synthesized using acetylene reactants. This method may
generally be written as
##STR00012##
[0041] In the acetylene synthesis, a compound of the formula
(XX.sup.1ML.sub.nL.sup.1.sub.m)p is reacted with an acetylene
compound of the formula R.sup.9CCR.sup.10, to yield an alkylidene
according to the present invention. R.sup.9 and R.sup.10 may be the
same or different and may be hydrogen, substituted or unsubstituted
alkyl, or substituted or unsubstituted aryl.
[0042] The ruthenium and osmium complexes of the present invention
may also be synthesized using cumulated olefins. This method may
generally be written as
##STR00013##
[0043] The ruthenium and osmium complexes of the present invention
may also be synthesized by a "one pot" method that can generally be
written as
##STR00014##
[0044] In this method, a compound of the formula
(X.sup.1ML.sub.nL.sup.1.sub.m)p is contacted with a diazo compound
of the formula RC(N.sub.2)R.sup.1 in the presence of a neutral
electron donor L.sup.2 to yield an alkylidene compound according to
the present invention.
[0045] The catalysts of the present invention are highly active in
metathesis reactions and may be used to catalyze a variety of
metathesis reactions including, but not limited to, ROMP of
strained and unstrained cyclic olefins, RCM of acyclic dienes,
self- and cross-metathesis reactions involving at least one acyclic
or unstrained cyclic olefin, depolymerization of olefinic polymers,
acyclic diene metathesis polymerization ("ADMET"), alkyne
polymerization, carbonyl olefination, and preparation of telechelic
polymers.
[0046] ROMP, RCM, cross metathesis, depolymerization, and
telechelic polymer reactions have been described in detail in U.S.
patent application Ser. No. 08/282,827. Those skilled in the art
can readily identify the appropriate conditions for carrying out
these reactions using the complexes of the present invention. Any
specific differences between the reactions disclosed in patent
application Ser. No. 08/282,827 and those of the present invention
are noted in the detailed descriptions given below.
[0047] Alkyne polymerization is described by R. Schlund et al. in
J. Am. Chem. Soc. 1989, 111, 8004-8006, and by L. Y. Park et al. in
Macromolecules 1991, 24 3489-3495, both of which are incorporated
herein by reference. Carbonyl olefination is described by K. A.
Brown-Wensley et al. in Pure Appl. Chem. 1983, 55, 1733-1744, by A.
Aguero et al. in J. Chem. Soc., Chem. Commun. 1986, 531-533, and by
G. C. Bazan et al. in Organometallics 1991, 10, 1062-1067, all of
which are incorporated herein by reference. ADMET is described by
K. B. Wagener et al. in Macromolecules 1991, 24, 2649-2657, which
is incorporated herein by reference. Those skilled in the art can
readily identify the appropriate conditions for carrying out these
reactions using the complexes of the present invention.
[0048] We now describe specific examples of the synthesis and
olefin metathesis reactions described above. For clarity, detailed
reaction conditions and procedures are described in the final,
"Experimental Procedures" section.
Synthesis of Alkylidene Complexes
Synthesis of RuCl.sub.2(.dbd.CHR)(PPh.sub.3).sub.2 Via Alkylidene
Transfer From Diazoalkanes (Complexes 1-9)
[0049] The alkylidene complexes of the present invention may be
synthesized by the reaction of RuCl.sub.2(PPh.sub.3).sub.3 with
alkyl, aryl, and diaryldiazoalkanes. Generally, the synthesis
reactions involve a spontaneous N.sub.2 evolution at -78.degree.
C., indicating rapid reaction of RuCl.sub.2(PPh.sub.3).sub.3 with
diazoethane, diazopropane or a para-substituted aryldiazoalkane of
the formula p-C.sub.6H.sub.4XCHN.sub.2 to give
RuCl.sub.2(.dbd.CHR)(PPh.sub.3).sub.2 (R.dbd.Me [complex 1], Et
[complex 2]) and
RuCl.sub.2(.dbd.CH-p-C.sub.6H.sub.4X)(PPh.sub.3).sub.2 (X.dbd.H
[complex 3], NMe.sub.2 [complex 4], OMe [complex 5], Me [complex
6], F [complex 7], Cl [complex 8], NO.sub.2 [complex 9]),
respectively (eq. 1). However, no reaction was observed with
diphenyldiazomethane or 9-diazofluorene at RT, and reaction with
diazomethane led to a complex mixture of unidentified products.
##STR00015##
[0050] Complexes 1-9 were isolated in 80-90% yield as green
air-stable solids. In all of these reactions, transfer of the
alkylidene moiety from the diazo compound to ruthenium was clearly
indicated by the characteristic downfield-resonances of
H.sub..alpha. and C.sub..alpha. of the alkylidene moiety. Table I
below lists selected NMR data for complexes 3-9.
TABLE-US-00001 TABLE I Complex X H.sub..alpha. J.sub.HP(Hz)
C.sub..alpha. J.sub.PC(Hz) 3 H 19.56.sup.a 10.2 310.12 11.4 4
NMe.sub.2 18.30 6.1 309.68 11.4 5 OMe 19.38.sup.a 8.7 309.20 10.7 6
Me 19.55.sup.a 9.6 309.17 10.9 7 F 19.24 9.0 307.51 11.4 8 Cl 19.27
9.2 307.34 10.6 9 NO.sub.2 19.47 10.8 313.43 11.2 Spectra taken in
CD.sub.2Cl.sub.2 (in ppm) unless indicated otherwise. .sup.aIn
C.sub.6D.sub.6 (in ppm).
[0051] In analogy to the structurally characterized vinyl
alkylidene RuCl.sub.2(.dbd.CH--CH.dbd.CPh.sub.2)(PPh.sub.3).sub.2
(Complex A), these resonances appear as triplets due to .sup.31P
coupling. These spectroscopic data suggest that the phosphines are
mutually trans and that the alkylidene unit lies in the
P--Ru--P-plane. Additionally, the chemical shifts of H.sub..alpha.
and C.sub..alpha. in complexes 3-9 are downfield compared to
RuCl.sub.2(.dbd.CH--CH.dbd.CPh.sub.2)(PPh.sub.3).sub.2 (Complex A)
(67 H.sub..alpha.=17.94, C.sub..alpha.=288.9 ppm), possibly
attributed to the relatively reduced conjugation of the alkylidene
unit of complexes 3-9. This phenomenon might also be responsible
for the relative instability of complexes 1-9 in solution. These
complexes decompose within several hours via bimolecular pathways
as evidenced by the formation of the corresponding disubstituted
olefins RCH.dbd.CHR(R.dbd.Me, Et, p-C.sub.6H.sub.4X).
Synthesis of RuCl.sub.2(.dbd.CH-p-C.sub.6H.sub.4X)(PCy.sub.3).sub.2
Via Phosphine Exchange (Complexes 10-16)
[0052] To broaden the synthetic utility of the triphenylphosphine
catalysts, analogous trialkylphosphine derivatives of complexes 3-9
were prepared by phosphine exchange. Treatment of complexes 3-9
with 2.2 equiv. tricyclohexylphosphine at RT afforded, after
work-up, RuCl.sub.2(.dbd.CH-p-C.sub.6H.sub.4X)(PCy.sub.3).sub.2
(X.dbd.H [complex 10], NMe2 [complex 11], OMe [complex 12], Me
[complex 13], F [complex 14], Cl [complex 15], NO.sub.2 [complex
16]), as purple (complex 11 is green) microcrystalline solids in
high yields according to the following reaction:
##STR00016##
[0053] The fully-characterized compounds were air-stable in the
solid state and did not show any signs of decomposition in solution
(CH.sub.2Cl.sub.2 or C.sub.6H.sub.6), even when heated to
60.degree. C. or in presence of alcohols, amines or water. Selected
solution NMR data for complexes 10-16 are listed in Table II. As
can be seen from this data, in contrast to the PPh.sub.3 complexes
3-9, no .sup.31P coupling was observed for the H.sub..alpha.
resonances of complexes 10-16 in the .sup.1H NMR. The chemical
shifts of these resonances are dependent on the electronic nature
of the X substituent.
TABLE-US-00002 TABLE II Complex X H.sub..alpha. C.sub..alpha.
J.sub.PC(Hz) 10 h 20.02 294.72 7.6 11 NMe.sub.2 18.77 286.13 a 12
OMe 19.48 290.90 a 13 Me 19.80 293.86 8.3 14 F 19.86 291.52 8.6 15
Cl 19.98 291.46 8.0 16 NO.sub.2 20.71 289.07 7.6 Spectra taken in
CD.sub.2Cl.sub.2 (in ppm). a broad signal
[0054] The lack of .sup.31P coupling suggests that the alkylidene
moiety is perpendicular to the P--Ru--P-plane as in
RuCl.sub.2(.dbd.CH--CH.dbd.CPh.sub.2)(PCy.sub.3).sub.2 (Complex B).
Also, the resonance shifts' dependency on the electronic nature of
the X substituent suggests a high degree of conjugation between the
carbene carbon and the aromatic ring of the benzylidene moiety.
One-Pot Synthesis of RuCl.sub.2(.dbd.CHPh)(PR.sub.3).sub.2
(Complexes 10, 17 And 18)
[0055] Due to the relative instability of the intermediate
RuCl.sub.2(.dbd.CHPh)(PPh.sub.3).sub.2 (complex 3) in solution,
RuCl.sub.2(.dbd.CHPh)(PCy.sub.3).sub.2 (complex 10) can be
synthesized in 75-80% yield from RuCl.sub.2(PPh.sub.3).sub.3.
However, avoiding isolation of complex 3 and adding
tricyclohexylphosphine at .apprxeq.-50.degree. C. shortly after
RuCl.sub.2(PPh.sub.3).sub.3 was treated with phenyldiazomethane,
complex 10 can be obtained in nearly quantitative yield in less
than 1 hour in a so-called "one pot synthesis". The same procedure
can also be applied to the synthesis of more soluble derivatives
including RuCl.sub.2(.dbd.CHPh)(PR.sub.3).sub.2 where R is Cp
(complex 17) or R is .sup.iPr (complex 18) that exhibit comparable
metathesis activity, according to the following reaction:
##STR00017##
Synthesis of Methylidene Complex
RuCl.sub.2(.dbd.CH.sub.2)(PCy.sub.3).sub.2 (Complex 19)
[0056] Whereas
RuCl.sub.2(.dbd.CH--CH.dbd.CPh.sub.2)(PCy.sub.3).sub.2 (Complex B)
reacts with ethylene under 100 psi pressure at 50.degree. C. in
CD.sub.2 Cl.sub.2 within several hours to reach an equilibrium of
RuCl.sub.2(.dbd.CH--CH.dbd.CPh.sub.2)(PCy.sub.3).sub.2 (Complex B)
and RuCl.sub.2(.dbd.CH.sub.2)(PCy.sub.3).sub.2 (complex 19) in a
ratio of 80:20, benzylidene RuCl.sub.2(.dbd.CHPh)PCy.sub.3).sub.2
(complex 10) is quantitatively converted to the methylidene complex
19 within a few minutes at RT under 14 psi of ethylene (eq. 7).
##STR00018##
[0057] Complex 19 is isolated as a red-purple, air-stable solid. A
pentacoordinate ruthenium center may be inferred from the analytic
and spectroscopic data. Methylidene complex 19 is less stable in
solution than benzylidene complex 10; decomposition is observed
after 12 hours in solution (CH.sub.2 Cl.sub.2, C.sub.6 H.sub.6).
The decomposition Fate increases as catalyst solutions are heated.
Among all isolated methylidene complexes including
RuCl(NO)(CH.sub.2)(PPh.sub.3).sub.2 and
Ir.dbd.CH.sub.2(N(SiMe.sub.2--CH.sub.2PPh.sub.2 (.sub.2), complex
19 is the first isolable metathesis-active methylidene complex.
Complex 19 has a high activity and exhibits a similar stability
towards functional groups as benzylidene complex 10, as shown in
the ROMP of cyclooctene and 1,5-cyclooctadiene and in ring-closing
metathesis of diethyldiallyl malonate.
Synthesis of Substituted Alkylidene Complexes Via Cross
Metathesis
[0058] The rapid reaction of RuCl.sub.2(.dbd.CHPh)(PCy.sub.3).sub.2
(complex 10) with ethylene to give
RuCl.sub.2(.dbd.CHPh)(PCy.sub.3).sub.2 (complex 19) has prompted
extension by the inventors of these metathesis studies to terminal
and disubstituted olefins. Although olefin metathesis is an
equilibrium process, the kinetic products may be isolated under
certain conditions. Indeed, complex 10 is quantitatively converted
to the alkylidenes according to the formula
RuCl.sub.2(.dbd.CHR)(PCy.sub.3).sub.2 [R.dbd.Me (complex 20),
R.dbd.Et (complex 21), R=n-Bu (complex 22)] when reacted with a
tenfold excess of propene, 1-butene or 1-hexene, respectively. In
each case, an equimolar amount of styrene was formed and
spectroscopically identified (eq. 4).
##STR00019##
[0059] The isolated compounds 20-22 are comparable to precursor
complex 10 in stability and solubility and reconvert to precursor
complex 10 in the presence of a large excess (30-50 equiv.) of
styrene. Metathesis of disubstituted olefins cis-2-butene and
cis-3-hexene leads to the formation of
RuCl.sub.2(.dbd.CHR)(PCy.sub.3).sub.2 from benzylidene complex 10.
However, due to the steric bulk of these olefins, the reactions
proceed considerably slower than with the corresponding terminal
olefins. No reaction occurred between precursor complex 10 and
3,3-dimethyl-1-butene, and the steric interaction between the metal
fragment and the incoming olefin is also presumed to be responsible
for the slow reaction with 20 equiv. 3-methyl-1-butene. The
expected alkylidene RuCl.sub.2(.dbd.CH .sup.iPr)(PCy.sub.3).sub.2
was identified by NMR, but its concentration remained small and
constant throughout the reaction. After 6 hours, initiation was
complete and methylidene complex 19 was isolated as the sole
reaction product. If alkylidene forms of
RuCl.sub.2(.dbd.CHR)(PCy.sub.3).sub.2 of complexes 20-22 are not
isolated immediately after formation, slow reaction with excess
olefin results in the formation of
RuCl.sub.2(.dbd.CH.sub.2)(PCy.sub.3).sub.2 (complex 19) within
10-15 hours (eq. 8).
##STR00020##
[0060] As proposed in the reaction scheme I below, complex 10 is
likely to react with a terminal olefin to rapidly form a
metallocyclobutane intermediate I, in that the two substituents (Ph
and R) are in 1,3-position for steric reasons. Productive cleavage
of the intermediate metallacycle leads to the formation of
alkylidene complexes 20-22 as kinetic products.
##STR00021##
[0061] On extended reaction times, alkylidene complexes
RuCl.sub.2(.dbd.CHR)(PCy.sub.3).sub.2 (complexes 20-22) undergo a
slow reaction with excess olefin to form methylidene complex 19
presumably through intermediate metallocyclobutane II.
RuCl.sub.2(.dbd.CH.sub.2)(PCy.sub.3).sub.2 (complex 19) appears to
be the thermodynamic product as it will not metathesize
.alpha.-olefins in dilute conditions.
Metathesis of Conjugated And Cumulated Olefins
[0062] Treatment of RuCl.sub.2(.dbd.CHPh)(PCy.sub.3).sub.2 (complex
10) with a tenfold excess of 1,3-butadiene and 1,2-propadiene
resulted in the high-yield formation of vinylalkylidene
RuCl.sub.2(.dbd.CH--CH.dbd.CH.sub.2)(PCy.sub.3).sub.2 (complex 23)
and vinylidene RuCl.sub.2(.dbd.C.dbd.CH.sub.2)(PCy.sub.3).sub.2
(complex 24), respectively (eq. 5). The former complex cannot be
synthesized via ring-opening of cyclopropene.
##STR00022##
[0063] The spectroscopic data for these complexes is similar to
those of related compounds
RuCl.sub.2(.dbd.CH--CH.dbd.CPh.sub.2)(PCy.sub.3).sub.2 (complex B)
and RuCl.sub.2(.dbd.C.dbd.CH-t-Bu)(PPh.sub.3).sub.2. In contrast to
observations made in the synthesis of
RuCl.sub.2(.dbd.CHR)(PCy.sub.3).sub.2 [R.dbd.Me (complex 20), Et
(complex 21), n-Bu (complex 22)], that no methylidene
RuCl.sub.2(.dbd.CH.sub.2)(PCy.sub.3).sub.2 (complex 19) was formed
at extended reaction times can be explained by the low activity of
complexes 23 and 24 towards their olefinic precursors. However,
both complexes 23 and 24 exhibit ROMP-activity that, in the case of
the former, was evidenced by comparatively slow polymerization of
cyclooctene (PDI=2.0). Vinylidene complex 24 rapidly polymerized
norbornene, although relatively slow initiation can be inferred by
the lack of the characteristic color change, and both compounds are
inactive for metathesis of acyclic olefins.
Introduction of Functional Groups Via Metathesis
[0064] Although less active than their early transition metal
counterparts, ruthenium alkylidenes have broader synthetic utility
due to their tolerance of functional groups and protic media. The
inventors have shown that vinylalkylidenes
RuCl.sub.2(.dbd.CH--CH.dbd.CPh.sub.2)(PR.sub.3).sub.2 (R.dbd.Ph,
complex A; or R.dbd.Cy, complex B) react readily with electron-rich
olefins, such as vinyl ethers H.sub.2 C.dbd.CH--OR', to yield
metathesis-inactive RuCl.sub.2(.dbd.CH--OR')(PR.sub.3).sub.2. This
irreversible reaction has been extensively utilized by the
inventors for the endcapping of growing polymer chains.
Electron-deficient olefins are not metathesized by the
triphenylphosphine catalyst
RuCl.sub.2(.dbd.CH--CH.dbd.CPh.sub.2)(PPh.sub.3).sub.2 (complex A),
and the tricyclohexylphosphine catalyst
RuCl.sub.2(.dbd.CH--CH.dbd.CPh.sub.2)(PCy.sub.3).sub.2 (complex B)
displays only limited activity towards these substrates. However,
the enhanced activity of the benzylidene catalyst complex 10
prompted further exploration of this reaction. As shown in eq. 6,
metathesis of functionalized olefins catalyzed by benzylidene
complex 10 is not limited to electron-rich olefins, such as allyl
acetate, but also includes electron-deficient alkenes, such as
allyl chloride. Benzylidene complex 10, will also undergo efficient
metathesis of unprotected en-ols, as shown with 4-pentene-1-ol, to
generate the corresponding hydroxy alkylidene
RuCl.sub.2(.dbd.CH(CH.sub.2).sub.3 OH)(PCy.sub.3).sub.2 (complex
27) (eq. 6).
##STR00023##
[0065] Compounds 25-27 were readily isolated and fully
characterized. In all cases the alkylidene H.sub..alpha. resonances
appeared as triplets due to coupling with the vicinal CH.sub.2
groups. Alkylidenes 25-27 are active in ROMP of low strained
olefins, which makes them attractive catalysts for the synthesis of
telechelic and other functionalized polymers.
Use of Alkylidene Complexes As Metathesis Catalysts
Kinetic Studies of the Polymerization of Norbornene Catalyzed By
RuCl.sub.2(.dbd.CH-p-C.sub.6H.sub.4X)(PPh.sub.3).sub.2 (Complexes
3-9)
[0066] Complexes 3-9 polymerize norbornene at a rate of .apprxeq.
150 equiv./hour in CH.sub.2Cl.sub.2 at RT to give polynorbornene in
quantitative yields. All reactions were accompanied by a
characteristic color change from green-brown to orange that
indicates complete initiation. The resulting polymers are
approximately 90% trans as determined by .sup.1H NMR. However, the
present catalysts produce nearly monodispersed polymers
(PDIs=1.04-1.10, compared to 1.25 for
RuCl.sub.2(.dbd.CH--CH.dbd.CPh.sub.2)(PPh.sub.3).sub.2) (complex
A), consistent with measured initiation rates. As observed for
RuCl.sub.2(.dbd.CH--CH.dbd.CPh.sub.2)(PPh.sub.3).sub.2 (complex A),
complexes 3-9 fulfill the general criteria for living systems since
the propagating alkylidene (.sup.1H NMR: .delta. 17.79 ppm (dt)) is
stable throughout the reaction, and the molecular weights of the
polymers display a linear dependence on the [catalyst]/[monomer]
ratio.
[0067] The influence of the para-substituents in the alkylidene
moiety on the metathesis activity was qualitatively assessed.
Catalysts based on complexes 3-9
(RuCl.sub.2(.dbd.CH-p=C.sub.6H.sub.4X)(PPh.sub.3).sub.2, [Ru]=0.022
M) were treated with norbornene ([monomer]=0.435 M) in CH.sub.2
Cl.sub.2 solution. The pseudo first-order rate constants for
initiation and propagation were obtained by integrating the
H.sub..alpha. resonances of complexes 3-9 against the corresponding
resonance of the propagating alkylidene species, and monitoring the
decreasing monomer concentration against an internal ferrocene
standard, respectively. The derived values of k.sub.i and k.sub.p
are listed in Table III.
TABLE-US-00003 TABLE III Initiation Rate Propagation Rate Constant,
k.sub.i Constant, k.sub.p Complex X (.times.10.sup.-3/mol sec
(.times.10.sup.-3/mol sec) k.sub.i/k.sub.p 3 H 11.5 1.28 9.0 4
NMe.sub.2 3.32 1.28 2.6 5 OMe 3.34 1.28 2.6 6 Me 3.69 1.28 2.9 7 F
6.19 1.28 4.8 8 Cl 1.56 1.28 1.2 9 NO.sub.2 2.91 1.28 2.3 a For
[Ru] = 0.022 M; [norbornene] = 0.435 M in C.sub.6D.sub.6 at
17.degree. C.
[0068] As can be seen in Table III, the electronic effect of X in
RuCl.sub.2(.dbd.CH-p-C.sub.6H.sub.4X)(PPh.sub.3).sub.2 on
initiation rate seems to be relatively small: the rate in the
fastest case (X.dbd.H [complex 3]) was approximately 10 times
higher than in the slowest (X.dbd.Cl [complex 8]). A general trend
concerning the electronic influence of the substituents X was not
observed. Under similar reaction conditions with
RuCl.sub.2(.dbd.CH--CH.dbd.CPh.sub.2)(PPh.sub.3).sub.2 (complex A)
as catalyst, observed initiation was <50%. When norbornene
consumption was complete, uninitiated carbene was spectroscopically
identified. The extrapolated ratio of
k.sub.i/k.sub.p=6.times.10.sup.-3 is approximately 1000 times
smaller than that observed for complexes 3-9. These results suggest
that conjugation seems to decrease k.sub.i, presumably by lowering
the ground state energy of the starting arylidenes for complexes
3-9 relative to the likely metallocyclobutane intermediate.
Although benzylidene forms of complexes 3-9 are better initiators
than RuCl.sub.2(.dbd.CH--CH.dbd.CPh.sub.2)(PPh.sub.3).sub.2
(Complex A), application of the former as metathesis catalysts is
similarly limited to ROMP of relatively high-strained cyclic
olefins, such as norbornene and cyclobutene derivatives, whose
calculated strain energies exceed 10-15 kcal/mol.
ROMP Activity of RuCl.sub.2(.dbd.CH-p-C.sub.6 H.sub.4
X)(PCy.sub.3).sub.2 (Complexes 10-16)
[0069] Benzylidenes
RuCl.sub.2(.dbd.CH-p-C.sub.6H.sub.4X)(PCy.sub.3).sub.2 (complexes
10-16) are extremely active ROMP-catalysts compared to their
PPh.sub.3 analogs complexes 3-9. Except for norbornene, ROMP of
highly strained monomers including functionalized norbornenes,
7-oxanorbornenes, and variously substituted cyclobutenes was proved
to be living and lead to polymers with exceptionally narrow
molecular weight distributions (PDIs<1.1). In analogy to
RuCl.sub.2(.dbd.CH--CH.dbd.CPh.sub.2)(PCy.sub.3).sub.2 (complex B),
complexes 10-16 can also polymerize low-strain cycloolefins, such
as cyclooctene and 1,5-cyclooctadiene. Although the corresponding
polymers are not monodispersed (PDI.apprxeq.1.50-1.60), these
polymerizations proceed more rapidly and with significantly lower
polydispersities than with
RuCl.sub.2(.dbd.CH--CH.dbd.CPh.sub.2)(PCy.sub.3).sub.2 (complex B)
as catalyst (PDI.apprxeq.2.50). However, the occurrence of
"back-biting" in these reactions causes broader PDIs. Therefore,
these polymerizations cannot be considered living, even though a
propagating alkylidene was observed for ROMP of cyclooctadiene by
.sup.1H NMR (.delta. 18.88 (t)) with complex 10.
[0070] Complex 10 also reacts with cyclooctatetraene in
CD.sub.2Cl.sub.2 with complete initiation, but propagation does not
occur, and facile back-biting leads to the formation of benzene.
The increased activity of complexes 10-16 compared to
RuCl.sub.2(.dbd.CH--CH.dbd.CPh.sub.2)(PCy.sub.3).sub.2 (Complex B)
is attributed to a faster initiation rate. Recently developed
catalyst mixtures containing [(cymene)RuCl.sub.2].sub.2, a bulky
tertiary phosphine and trimethylsilyldiazomethane were found to
catalyze ROMP of cyclooctenes.
Metathesis of Acyclic Olefins
[0071] The inventors recently showed that vinylalkylidene
RuCl.sub.2(.dbd.CH--CH.dbd.CPh.sub.2)(PCy.sub.3).sub.2 (Complex B)
exhibits metathesis activity towards acyclic olefins, e.g.,
cis-2-pentene. Although the turnover-numbers were modest compared
to the best of the tungsten and molybdenum-based catalysts,
vinylalkylidene
RuCl.sub.2(.dbd.CH--CH.dbd.CPh.sub.2)(PCy.sub.3).sub.2 (complex B)
was the first example of acyclic metathesis induced by a ruthenium
carbene complex. However, slow initiation was a present limitation
for its general use as a catalyst. Due to their exceptionally high
activity in ROMP, complexes 10-16 were found to be efficient
acyclic metathesis catalysts, as representatively shown with
benzylidene RuCl.sub.2(.dbd.CHPh)(PCy.sub.3).sub.2 (complex 10),
discussed below.
Kinetic Studies With RuCl.sub.2(.dbd.CH-p-C.sub.6 H.sub.4
X)(PCy.sub.3).sub.2 (Complexes 10-16)
[0072] The electronic influence of X on the initiation rates of
RuCl.sub.2(.dbd.CH-p-C.sub.6H.sub.4X)(PCy.sub.3).sub.2 (complexes
10-16) was probed by examining their reactions with 1-hexene. Clean
and quantitative conversion to the pentylidene
RuCl.sub.2(.dbd.CH-n-Bu)(PCy.sub.3).sub.2 complex 22 was observed
in all cases. Pseudo first-order rate constants were measured by
integration of the H.sub..alpha. resonances of benzylidene
complexes 10-16 versus pentylidene complex 22. Representative plots
are shown in FIGS. 1A and 1B, and initiation rate constants
(k.sub.i) are listed in Table IV.
TABLE-US-00004 TABLE IV Initiation Rate Constant Complex X
k.sub.i[10.sup.-3](1/mol sec) 10 H 2.87 11 NMe.sub.2 0.31 12 OMe
1.01 3 Me 2.15 14 F 1.21 15 Cl 1.37 16 NO.sub.2 1.77 a For [Ru] =
0.01 M; [1-hexene] = 0.32 M in CD.sub.2Cl.sub.2 at T = 0.degree.
C.
[0073] As observed for living-ROMP of norbornene with catalysts
RuCl.sub.2(.dbd.CH-p-C.sub.6H.sub.4X)(PPh.sub.3).sub.2 (complexes
3-9), the range of k.sub.is among the substituted benzylidenes is
approximately an order of magnitude. Although no general trend can
be discerned, any perturbation to the aromatic .pi.-system (i.e.,
X.noteq.H) decreases the initiation rate.
RuCl.sub.2(.dbd.CHPh)(PCy.sub.3).sub.2 (complex 10) initiated
approximately 1000 times faster than vinylidene
RuCl.sub.2(.dbd.CH--CH.dbd.CPh.sub.2)(PCy.sub.3).sub.2 (Complex B)
which did not completely react to give pentylidene complex 22 under
the above-mentioned conditions.
Structure of Exemplary Complex
X-Ray Diffraction Study of
RuCl.sub.2(.dbd.CH-p-C.sub.6H.sub.4Cl)(PCy.sub.3).sub.2 (Complex
15)
[0074] Representative of complexes 10-16, the structure of the
Cl-substituted benzylidene
RuCl.sub.2(.dbd.CH-p-C.sub.6H.sub.4Cl)(PCy.sub.3).sub.2 was further
confirmed by a single crystal X-ray diffraction study. An ORTEP
drawing of this complex is shown in FIG. 2, and selected bond
lengths and angles are given in Table V below. The analysis reveals
distorted square-pyramidal coordination with a nearly linear
Cl(1)-Ru--Cl(2) angle (167.61.degree.). The carbene unit is
perpendicular to the P1-Ru-P2 plane, and the aryl ligand is only
slightly twisted out of the Cl1-Ru-Cl2 plane. The Ru--Cl bond
distance is shorter (1.838 (3) .ANG.) than in related compounds
RuCl.sub.2(.dbd.CH--CH.dbd.CPh.sub.2)(PCy.sub.3).sub.2
[d(Ru--C)=1.851 (21)] or
RuCl(.dbd.C(OMe)--CH.dbd.CPh.sub.2)(CO)(Pi-Pr.sub.3).sub.2
[RuCl.sub.2(.dbd.CH--CH.dbd.CPh.sub.2)(PCy.sub.3).sub.2
F.sub.4][d-(Ru--C)=1.874 (3), respectively.
TABLE-US-00005 TABLE V Bond Lengths [.ANG.] Ru--C1 1.839(3) Ru--Cl1
2.401(1) Ru--Cl2 2.395(1) Ru--P1 2.397(1) Ru--P2 2.435(1) Bond
Angles [.degree.] Cl1-Ru--P1 87.2(1) P1-Ru--C1 97.5(1) P1-Ru--Cl2
91.5(1) Cl1-Ru--P2 90.8(1) C1-Ru--P2 101.2(1) Cl1-Ru--C1 88.7(1)
Cl1-Ru--Cl2 167.6(1) C1-Ru--Cl2 103.7(1) P1-Ru--P2 161.1(1)
Cl2-Ru--P2 86.5(1)
Experimental Section
General Experimental Procedures
[0075] All manipulations were performed using standard Schlenk
techniques under an atmosphere of argon. Argon was purified by
passage through columns of BASF R3-11 catalyst (Chemalog) and 4
.ANG. molecular sieves (Linde). Solid organometallic compounds were
transferred and stored in a nitrogen-filled Vacuum Atmospheres
drybox or under an atmosphere of argon. NMR spectra were recorded
with either a QE-300 Plus (300.1 MHz .sup.1H; 75.5 MHz .sup.13C), a
JEOL GX-400 (399.7 MHz .sup.1H; 161.9 MHz .sup.31P) or a Bruker AM
500 (500.1 MHz .sup.1H; 125.8 MHz .sup.13C; 202.5 MHz .sup.31P;
470.5 MHz .sup.19F) spectrometer.
[0076] Methylene chloride and benzene were passed through columns
of activated alumina and stored under argon. Benzene-d.sub.6 and
methylene chloride-d.sub.2 were degassed by three continuous
freeze-pump-thaw cycles. RuCl.sub.2(PPh.sub.3).sub.3,
tricyclohexylphosphine, and the diazoalkanes H.sub.2CN.sub.2,
MeCHN.sub.2, EtCHN.sub.2, PhCHN.sub.2, p-C.sub.6H.sub.4NMe.sub.2
CHN.sub.2, p-C.sub.6H.sub.4 OMeCHN.sub.2,
p-C.sub.6H.sub.4MeCHN.sub.2, p-C.sub.6H.sub.4FCHN.sub.2,
p-C.sub.6H.sub.4 ClCHN.sub.2 and p-C.sub.6H.sub.4NO.sub.2CHN.sub.2
were prepared according to literature procedures. Norbornene was
dried over sodium, vacuum transferred and stored under argon.
Cyclooctene, 1,5-cyclooctadiene, and 1,3,5,7-cyclooctatetraene were
dried over CaH.sub.2, distilled and stored under argon. The
following chemicals were obtained from commercial sources and used
as received: ethylene, propylene, 1-butene, cis-2-butene, 1-hexene,
cis-3-hexene, 3-methyl-1-butene, 3,3-dimethyl-1-butene,
1,3-butadiene, 1,2-propadiene, allyl acetate, allyl chloride,
4-pentene-2-ol, diethyl diallyl malonate, triisopropylphosphine,
tricyclopentylphosphine, pentane, ether, acetone, and methanol.
Synthesis of RuCl.sub.2(.dbd.CHMe)(PPh.sub.3).sub.2 and
RuCl.sub.2(.dbd.CHEt)(PPh.sub.3).sub.2 (Complexes 1 And 2)
[0077] A solution of RuCl.sub.2(PPh.sub.3).sub.3 (417 mg, 0.43
mmol) in CH.sub.2Cl.sub.2 (10 mL) was treated at -78.degree. C.
with a -50.degree. C. 0.50 M solution of diazoethane (1.90 mL, 0.93
mmol, 2.2 eq.) in ether. Upon addition of diazoethane, a color
change from orange-brown to green-brown and slight bubbling were
observed. After the cooling bath was removed, the solution was
stirred for 3 min and then evaporated to dryness. The oily residue
was washed several times with small quantities of ice-cold ether (3
mL portions) and the remaining olive-green solid
RuCl.sub.2(.dbd.CHMe)(PPh.sub.3).sub.2 was dried under vacuum for
several hours. Yield=246 mg (78%). .sup.1H NMR (CD.sub.2 Cl.sub.2):
.delta. 18.47 (tq, J.sub.PH=10.2 Hz, .sup.3J.sub.HH=5.1 Hz,
Ru.dbd.CH), 7.68-7.56 and 7.49-7.36 (both m, P(C.sub.6
H.sub.5).sub.3), 2.59 (d, .sup.3J.sub.HH 5.1 Hz, CH.sub.3).
.sup.13C NMR (CD.sub.2Cl.sub.2): .delta. 320.65 (t, J.sub.PC=9.9
Hz, Ru.dbd.CH), 134.76 (m, o-C of P(C.sub.6 H.sub.5).sub.3), 132.06
(m, ipso-C of P(C.sub.6 H.sub.5).sub.3), 130.38 (s, p-C of
P(C.sub.6 H.sub.5).sub.3), 128.44 (m, m-C of
P(C.sub.6H.sub.5).sub.3). .sup.31P NMR (CD.sub.2Cl.sub.2): .delta.
29.99 (s, PPh.sub.3). Anal. Calcd. for C.sub.38H.sub.34 Cl.sub.2
P.sub.2 Ru: C, 62.99; H, 4.73. Found: C, 63.12; H, 4.61.
[0078] In an analogous procedure,
RuCl.sub.2(.dbd.CHEt)(PPh.sub.3).sub.2 was prepared, starting with
RuCl.sub.2(PPh.sub.3).sub.3 (502 mg, 0.52 mmol) and a 0.45 M
solution of diazopropane (2.56 mL, 1.15 mmol, 2.2 eq.) in ether. An
orange-brown microcrystalline solid was obtained. Yield=311 mg
(81%). .sup.1H NMR (C.sub.6D.sub.6): .delta. 18.21 (tt,
J.sub.PH=10.8, 3J.sub.HH 6.6 Hz, Ru.dbd.CH), 7.91-7.86 and
6.97-6.80 (both m, P(C.sub.6H.sub.5).sub.3), 3.11 (dq,
.sup.3J.sub.HH=.sup.3J.sub.HH'=6.6 Hz, CH.sub.2 CH.sub.3), 0.79 (t,
.sup.3J.sub.HH=6.6 Hz, CH.sub.2CH.sub.3). .sup.13C NMR
(CD.sub.2Cl.sub.2): .delta. 320.88 (t, J.sub.PC=10.0 Hz,
Ru.dbd.CH), 134.36 (m, o-C of P(C.sub.6H.sub.5).sub.3, 132.27 (m.
ipso-C of P(C.sub.6H.sub.5).sub.3), 129.89 (s, p-C of
P(C.sub.6H.sub.5).sub.3), 128.14 (m, m-C of
P(C.sub.6H.sub.5).sub.3), 53.20 (s, CH.sub.2CH.sub.3), 29.74 (s,
CH.sub.2CH.sub.3). .sup.31P NMR (CD.sub.2Cl.sub.2): .delta. 30.02
(s, PPh.sub.3). Anal. Calcd. for C.sub.39H.sub.38Cl.sub.2P.sub.2Ru:
C, 63.42; H, 4.91. Found: C, 62.85; H, 4.81.
Synthesis of RuCl.sub.2(.dbd.CHPh)(PPh.sub.3).sub.2 (Complex 3)
[0079] A solution of RuCl.sub.2(PPh.sub.3).sub.3 (2.37 g, 2.47
mmol) in CH.sub.2 Cl.sub.2 (20 mL) was treated at -78.degree. C.
with a -50.degree. C. solution of phenyldiazomethane (584 mg, 4.94
mmol, 2.0 eq.) in CH.sub.2Cl.sub.2 or pentane (3 mL). A spontaneous
color change from orange-brown to brown-green and vigorous bubbling
were observed. After the cooling bath was removed, the solution was
stirred for 5 min and the solution was then concentrated to
.about.3 mL. Upon addition of pentane (20 mL), a green solid was
precipitated, separated from the brown mother-liquid via cannula
filtration, dissolved in CH.sub.2Cl.sub.2 (3 mL) and reprecipitated
with pentane. This procedure was repeated until the mother- liquid
was nearly colorless. The remaining grey-green microcrystalline
solid was dried under vacuum for several hours. Yield=1.67 g (89%).
.sup.1H NMR (C.sub.6D.sub.6): .delta. 19.56 (t, J.sub.PH=10.2 Hz,
Ru.dbd.CH), 7.80-7.64 and 6.99-6.66 (both m, C.sub.6H.sub.6 and
P(C.sub.6H.sub.5).sub.3). .sup.13C NMR (CD.sub.2Cl.sub.2): .delta.
310.12 (t, J.sub.PC=11.4 Hz, Ru.dbd.CH), 155.36 (s, ipso-C of
C.sub.6H.sub.5), 134.91 (m, m-C or o-C of P(C.sub.6H.sub.5).sub.3),
133.97 (d, J.sub.PC 19.6 Hz, ipso-C of P(C.sub.6H.sub.5).sub.3),
130.44 (s, p-C of P(C.sub.6H.sub.5).sub.3), 130.03, 128.71 and
127.09 (all s, C.sub.6H.sub.5), 128.37 (s(br.), m-C or o-C of
P(C.sub.6H.sub.5).sub.3). .sup.31P NMR (CD.sub.2Cl.sub.2): .delta.
30.63 (s, PPh.sub.3). Anal. Calcd. for
C.sub.43H.sub.38Cl.sub.2P.sub.2Ru: C, 65.65; H, 4.61; P. 7.87.
Found: C, 65.83; H, 4.59; P. 7.93.
Synthesis of RuCl.sub.2(.dbd.CH-p-C.sub.6 H.sub.4
NMe.sub.2)(PPh.sub.3).sub.2 (Complex 4)
[0080] A solution of RuCl.sub.2(PPh.sub.3).sub.3 (466 mg, 0.49
mmol) in CH.sub.2Cl.sub.2 (10 mL) was treated at -78.degree. C.
with a -50.degree. C. solution of
p-C.sub.6H.sub.4NMe.sub.2CHN.sub.2 (160 mg, 0.98 mmol, 2.0 eq.) in
CH.sub.2Cl.sub.2 (3 mL). A spontaneous color change from
orange-brown to brown-green and vigorous bubbling was observed.
After the cooling bath was removed, the solution was stirred for 10
min and then the solvent was removed under vacuum. The brown
residue was dissolved in minimal amounts of CH.sub.2Cl.sub.2 (3
mL), and pentane (20 mL) was added to precipitate a green solid.
After cannula filtration, this procedure was repeated until the
filtrate was colorless. The remaining olive-green microcrystalline
solid was dried under vacuum for several hours. Yield=317 mg (78%).
.sup.1H NMR (CD.sub.2Cl.sub.2): .delta. 18.30 (t, J.sub.PH=6.1 Hz,
Ru.dbd.CH), 7.64 (d, .sup.3J.sub.HH=8.7 Hz, o-H of
C.sub.6H.sub.4NMe.sub.2), 7.52-7.49 (m, o-H of
P(C.sub.6H.sub.5).sub.3), 7.42 (t, .sup.3J.sub.HH=7.5 Hz, p-H of
P(C.sub.6 H.sub.5).sub.3, 7.33 (t, .sup.3J.sub.HH=7.5 Hz, m-H of
P(C.sub.6H.sub.5).sub.3), 6.32 (d, .sup.3J.sub.HH=8.7 Hz, m-H of
C.sub.6H.sub.4NMe.sub.2), 2.96 (s, N(CH.sub.3).sub.2). .sup.13C NMR
(CD.sub.2Cl.sub.2): .delta. 309.68 (t, J.sub.PC 11.4 Hz,
Ru.dbd.CH), 152.72 (s, ipso-C of C.sub.6H.sub.4NMe.sub.2), 135.01
(m, m-C or o-C of P(C.sub.6H.sub.5).sub.3), 133.57 (s, o-C or m-C
of C.sub.6H.sub.4NMe.sub.2), 131.86 (s, C of
P(C.sub.6H.sub.5).sub.3), 130.20 (s, o-C or m-C of
C.sub.6H.sub.4NMe.sub.2), 128.27 (m, m-C or o-C of
P(C.sub.6H.sub.5).sub.3), 127.54 (s(br.), p-C of
C.sub.6H.sub.4NMe.sub.2), 110.61 (d, J.sub.PC=21.5 Hz, ipso-C of
P(C.sub.6H.sub.5).sub.3, 40.30 (s, N(CH.sub.3).sub.2. .sup.31P NMR
(CD.sub.2Cl.sub.2): .delta. 34.84 (s, PPh.sub.3). Anal. Calcd. for
C.sub.45H.sub.41Cl.sub.2NP.sub.2Ru: C, 65.14; H, 4.98; N, 1.69.
Found: C, 65.28; H, 4.97; N 1.80.
Synthesis of RuCl.sub.2(.dbd.CH-p-C.sub.6 H.sub.4
OMe)(PPh.sub.3).sub.2 (Complex 5)
[0081] A solution of RuCl.sub.2(PPh.sub.3).sub.3 (561 mg, 0.59
mmol) in CH.sub.2Cl.sub.2 (12 mL) was treated at -78.degree. C.
with a -40.degree. C. solution of p-C.sub.6H.sub.4 OMeCHN.sub.2 (87
mg, 0.59 mmol, 1.0 eq.) in CH.sub.2Cl.sub.2 (3 mL). A spontaneous
color change from orange-brown to brown-green and vigorous bubbling
was observed. After the cooling bath was removed, the solution was
stirred for 5 min and then the solvent was removed under vacuum.
The brown-green residue was dissolved in minimal amounts of
CH.sub.2Cl.sub.2 (2 mL), and pentane (20 mL) was added to
precipitate a brown solid. The brown-green solution was separated
via cannula filtration and dried under vacuum. The remaining
olive-green solid, complex 5, was repeatedly washed with ether (10
mL portions) and dried under vacuum for several hours. Yield w. 400
mg (83%). .sup.1H NMR,(C.sub.6D.sub.6): .delta. 19.39 (t,
J.sub.PH=8.7 Hz, Ru.dbd.CH), 7.85-7.72 and 7.03-6.80 (both m,
C.sub.6H.sub.4OMe and P(C.sub.6H.sub.5).sub.3, 6.41 (d,
.sup.3J.sub.HH=8.7 Hz, m-H of C.sub.6 H.sub.4 OMe), 3.22 (s,
OCH.sub.3). .sup.13C NMR (CD.sub.2Cl.sub.2); .delta. 309.20 (t,
J.sub.PC=10.7 Hz, Ru.dbd.CH), 147.42 (s, ipso-C of
C.sub.6H.sub.4OMe), 135.56 (pseudo-t, m-C or o-C of
P(C.sub.6H.sub.6).sub.3, 133.98 (s, o-C or m-C of
C.sub.6H.sub.4OMe), 131.46 (s, p-C of P(C.sub.6H.sub.5).sub.3),
130.43 (s, o-C or m-C of C.sub.6H.sub.4OMe), 128.40 (pseudo-t, m-C
or o-C of P(C.sub.6 H.sub.5).sub.3, 126.82 (s, p-C of
C.sub.6H.sub.4OMe), 113.95 (d, J.sub.PC=21.4 Hz, ipso-C of
P(C.sub.6H.sub.5).sub.3, 55.77 (s, OCH.sub.3). .sup.31P NMR
(CD.sub.2Cl.sub.2): .delta. 32.50 (s, PPh.sub.3). Anal. Calcd. for
C.sub.44H.sub.38Cl2OP.sub.2Ru: C, 64.71; H, 4.69. Found: C, 65.23;
H, 4.78.
Synthesis of
RuCl.sub.2(.dbd.CH-p-C.sub.6H.sub.4Me)(PPh.sub.3).sub.2 (Complex
6)
[0082] In a technique analogous to that used in synthesizing
complex 5, RuCl.sub.2(.dbd.CH-p-C.sub.6H.sub.4Me)(PPh.sub.3).sub.2
was prepared from RuCl.sub.2(PPh.sub.3).sub.3 (350 mg, 0.37 mmol)
and p-C.sub.6H.sub.4MeCHN.sub.2 (48 mg, 0.37 mmol, 1.0 eq.) A brown
microcrystalline solid was obtained. Yield=258 mg (87%). .sup.1H
NMR (C.sub.6 D.sub.6): .delta.519.55 (t, J.sub.PH=9.6 Hz,
Ru.dbd.CH), 7.84-7.63 and 7.02-6.80 (both m, C.sub.6H.sub.4Me and
P(C.sub.6H.sub.5).sub.3), 6.53 (d, .sup.3J.sub.HH=7.8 Hz, m-H of
C.sub.6H.sub.4 Me), 1.68 (s, CH.sub.3). .sup.13C NMR (CD.sub.2
Cl.sub.2): .delta. 309.17 (t, J.sub.PC=10.9 Hz, Ru.dbd.CH), 153.34
(s, ipso-C of C.sub.6H.sub.4Me), 135.50 (s, o-C or m-C of
C.sub.6H.sub.4OMe), 134.96 (m, m-C or o-C of
P(C.sub.6H.sub.5).sub.3, 132.13 (s, p-C of
P(C.sub.6H.sub.5).sub.3), 130.39 (s, o-C or m-C of
C.sub.6H.sub.4Me), 128.34 (m, m-C or o-C of
P(C.sub.6H.sub.5).sub.3), 126.76 (s, p-C of C.sub.6H.sub.4Me),
115.23 (d, J.sub.PC=21.4 Hz, ipso-C of P(C.sub.6 H.sub.5).sub.3),
40.92 (s, CH.sub.3). .sup.31P NMR (CD.sub.2Cl.sub.2): .delta. 31.29
(s, PPh.sub.3). Anal. Calcd. for C.sub.44H.sub.38Cl.sub.2P.sub.2Ru:
C, 66.00; H, 4.78. Found: C, 65.90; H, 4.75.
Synthesis of RuCl.sub.2(.dbd.CH-p-C.sub.6H.sub.4
F)(PPh.sub.3).sub.2 (Complex 7)
[0083] In a technique analogous to that used in synthesizing
complex 3, RuCl.sub.2(.dbd.CH-p-C.sub.6H.sub.4F)(PPh.sub.3).sub.2
was prepared from RuCl.sub.2(PPh.sub.3).sub.3 (960 mg, 1.00 mmol)
and p-C.sub.6H.sub.4FCHN.sub.2 (272 mg, 2.00 mmol, 2.0 eg.).
Complex 7 was synthesized in analogy to complex 3. An olive-green
microcrystalline solid was obtained. Yield=716 mg (89%). .sup.1H
NMR (CD.sub.2Cl.sub.2): .delta. 19.24 (t, J.sub.PH=9.0 Hz,
Ru.dbd.CH), 7.65-7.62 (m, o-H of C.sub.6H.sub.4F), 7.50-7.44 and
7.35-7.32 (both m, P(C.sub.6H.sub.5).sub.3, 6.62 (t,
.sup.3J.sub.HH=.sup.3J.sub.HF=8.9 Hz, m-H of C.sub.6H.sub.4F),
152.21 (s, ipso-C of C.sub.6H.sub.4F), 134.95 (m, m-C or o-C of
P(C.sub.6H.sub.5).sub.3), 134.04 (d, J.sub.CF=19.5 Hz, m-C of
C.sub.6H.sub.4F), 130.56 (s, p-C of P(C.sub.6H.sub.5).sub.3),
130.08 (d, J.sub.CF=8.7 Hz, o-C of C.sub.6H.sub.4F), 128.47 (m, m-C
or o-C of P(C.sub.6H.sub.5).sub.3, 115.67 (d, J.sub.PC=21.8 Hz,
ipso-C of P(C.sub.6H.sub.5).sub.3). .sup.31P NMR (CD.sub.2
Cl.sub.2): .delta. 31.03 (s, PPh.sub.3). .sup.19F NMR
(CD.sub.2Cl.sub.2): .delta. 45.63 (s, C.sub.6H.sub.4F). Anal.
Calcd. for C.sub.43H.sub.35Cl.sub.2FP.sub.2 Ru: C, 64.18; H 4.38.
Found: C, 64.42; H, 4.42.
Synthesis of
RuCl.sub.2(.dbd.CH-p-C.sub.6H.sub.4Cl)(PPh.sub.3).sub.2 (Complex
8)
[0084] In a technique analogous to that used in example 2,
RuCl.sub.2(.dbd.CH-p-C.sub.6H.sub.4Cl)(PPh.sub.3).sub.2 was
prepared from RuCl.sub.2(PPh.sub.3).sub.3 (350 mg, 0.37 mmol) and
p-C.sub.6H.sub.4ClCHN.sub.2 (111 mg, 0.73 mmol, 2.0 eq.) A green
microcrystalline solid was obtained. Yield=246 mg (82%). .sup.1H
NMR (CD.sub.2 Cl.sub.2); .delta. 19.27 (t, J.sub.PH=9.2 Hz,
Ru.dbd.CH), 7.51-7.44, 7.35-7.32 and 6.67-6.63 (all m,
C.sub.6H.sub.4Cl and P(C.sub.6H.sub.5).sub.3), 6.86 (d,
.sup.3J.sub.HH=8.8 Hz, m-H of C.sub.6H.sub.4Cl). .sup.13C NMR
(CD.sub.2Cl.sub.2): .delta. 307.34 (t, J.sub.PC=10.6 Hz, Ru--CH),
153.82 (s, ipso-C of C.sub.6H.sub.4Cl), 134.91 (m, m-C or o-C of
P(C.sub.6H.sub.5).sub.3), 130.58 (s, p-C of
P(C.sub.6H.sub.5).sub.3, 128.87, 128.81 and 127.85 (all s,
C.sub.6H.sub.4Cl), 128.48 (s(br.), m-C or o-C of
P(C.sub.6H.sub.5).sub.3, 115.90 (d, J.sub.PC=21.7 Hz, ipso-C of
P(C.sub.6H.sub.5).sub.3). .sup.31P NMR (CD.sub.2Cl.sub.2): .delta.
30.47 (s, PPh.sub.3). Anal. Calcd. for
C.sub.43H.sub.35Cl.sub.3P.sub.2Ru: C, 62.90; H. 4.30. Found: C,
62.87; H, 4.40.
Synthesis of
RuCl.sub.2(.dbd.CH-p-C.sub.6H.sub.4NO.sub.2)(PPh.sub.3).sub.2
(Complex 9)
[0085] In a technique analogous to that used in synthesizing
complex 3, RuCl.sub.2(.dbd.CH-p-C.sub.6H.sub.4
NO.sub.2)(PPh.sub.3).sub.21 complex 9 was prepared from
RuCl.sub.2(PPh.sub.3).sub.3 (604 mg, 0.63 mmol) and
p-C.sub.6H.sub.4NO.sub.2CHN.sub.2 (206 mg, 1.25 mmol, 2.0 eq.) A
tan microcrystalline solid was obtained. Yield=398 mg (76%).
.sup.1H NMR (CD.sub.2Cl.sub.2): .delta. 19.47 (t, J.sub.PH=10.8 Hz,
Ru.dbd.CH), 7.88-7.67, 7.38-7.33 and 7.02-6.71 (all m,
C.sub.6H.sub.4NO.sub.2 and P(C.sub.6H.sub.5).sub.3. .sup.13C NMR
(CD.sub.2Cl.sub.2): .delta. 313.43 (t, J.sub.PC=11.2 Hz,
Ru.dbd.CH), 158.40 (s, ipso-C of C.sub.6H.sub.4NO.sub.2), 148.11
(s, p-C of C.sub.6H.sub.4NO.sub.2), 135.49 (m, m-C or o-C of
P(C.sub.6H.sub.5).sub.3), 132.21 (s, m-C of
C.sub.6H.sub.4NO.sub.2), 130.91 (s, p-C of P(C.sub.6H.sub.5).sub.3,
130.72 (s, o-C of C.sub.6H.sub.4NO.sub.2), 128.86 (m, m-C or o-C of
P(C.sub.6H.sub.4).sub.3, 116.03 (d, J.sub.PC=21.6 Hz, ipso-C of
P(C.sub.6H.sub.5).sub.3). .sup.31P NMR (CD.sub.2Cl.sub.2): .delta.
32.27 (s, PPh.sub.3). Anal. Calcd. for C.sub.43 H.sub.35 Cl.sub.2
NO.sub.2 P.sub.2 Ru: C, 62.10; H, 4.24; N, 1.68. Found: C, 62.31;
H, 4.66; N, 1.84.
Synthesis of RuCl.sub.2(.dbd.CHPh)(PCy.sub.3).sub.2 (Complex
10)
[0086] A solution of RuCl.sub.2(.dbd.CHPh)(PPh.sub.3).sub.2 (242
mg, 0.31 mmol) in CH.sub.2 Cl.sub.2 (10 mL) was treated with a
solution of tricyclohexylphosphine (190 mg, 0.68 mmol; 2.2 eq.) in
CH.sub.2Cl.sub.2 (3 mL) and stirred at RT for 30 min. The solution
was filtered, and the solvent was removed under vacuum. The residue
was repeatedly washed with acetone or methanol (5 mL portions) and
dried in vacuo. A purple microcrystalline solid was obtained. Yield
290 mg (89%). .sup.1H NMR (CD.sub.2Cl.sub.2): .delta. 20.02 (s,
Ru.dbd.CH) (s, Ru.dbd.CH), 8.44 (d, .sup.3J.sub.HH=7.6 Hz, o-H of
C.sub.6H.sub.5), 7.56 (t, 3 J.sub.HH=7.6 Hz, p-H of
C.sub.6H.sub.5), 7.33 (t, .sup.3J.sub.HH=7.6 Hz, m-H of
C.sub.6H.sub.5), 2.62-2.58, 1.77-1.67, 1.46-1.39 and 1.25-1.16 (all
m, P(C.sub.6H.sub.11).sub.3. .sup.13 C NMR (CD.sub.2Cl.sub.2):
.delta. 294.72 (s, Ru.dbd.CH), 153.17 (s, ipso-C of
C.sub.6H.sub.5), 131.21, 129.49 and 129.27 (all s, C.sub.6
H.sub.5), 32.49 (pseudo-t, J.sub.app=9.1 Hz, ipso-C of
P(C.sub.6H.sub.11).sub.3), 30.04 (s, m-C of
P(C.sub.6H.sub.11).sub.3, 28.24 (pseudo-t, J.sub.app=4.5 Hz, o-C of
P(C.sub.6H.sub.11).sub.3), 26.96 (s, p-C of
P(C.sub.6H.sub.11).sub.3). .sup.31P NMR (CD.sub.2Cl.sub.2): .delta.
36.61 (s, PCy.sub.3). Anal. Calcd. for
C.sub.43H.sub.72Cl.sub.2P.sub.2Ru: C, 62.76; H, 8.82. Found: C,
62.84; H, 8.71.
One-Pot Synthesis of RuCl.sub.2(.dbd.CHPh)(PCy.sub.3).sub.2
(Complex 10)
[0087] A solution of RuCl.sub.2(PPh.sub.3).sub.3 (4.0 g, 4.17 mmol)
in CH.sub.2 Cl.sub.2 (40 mL) was treated at -78.degree. C. with a
-50.degree. C. solution of phenyldiazomethane (986 mg, 8.35 mmol,
2.0 eq.) in pentane (10 mL). Upon addition of the diazo compound,
an instantaneous color change from orange-brown to green-brown and
vigorous bubbling was observed. After the reaction mixture was
stirred at -70.degree. C. to -60.degree. C. for 5-10 min, an
ice-cold solution of tricyclohexylphosphine (2.57 g, 9.18 mmol, 2.2
eq.) in CH.sub.2Cl.sub.2 was added via syringe. Accompanied by a
color change from brown-green to red, the solution was allowed to
warm to RT and stirred for 30 min. The solution was filtered,
concentrated to half of the volume and filtrated. Methanol (100 mL)
was added to precipitate a purple microcrystalline solid, complex
10, that was filtered off, washed several times with acetone and
methanol (10 mL portions), and dried under vacuum for several
hours. Yield 3.40 g (99%).
Synthesis of
RuCl.sub.2(.dbd.CH-p-C.sub.6H.sub.4NMe.sub.2)(PCy.sub.3).sub.2
(Complex 11)
[0088] Starting with
RuCl.sub.2(.dbd.CH-p-C.sub.6H.sub.4NMe.sub.2)(PPh.sub.3).sub.2 (316
mg, 0.38 mmol) and tricyclohexylphosphine (235 mg, 0.84 mmol, 2.2
eq.) RuCl.sub.2(.dbd.CH-p-C.sub.6H.sub.4NMe.sub.2)(PCy.sub.3).sub.2
was obtained as a green microcrystalline solid in a procedure
analogous to that used in synthesizing complex 10. Yield 284 mg
(86%). .sup.1H NMR (CD.sub.2Cl.sub.2): .delta. 18.77 (s,
Ru.dbd.CH), 8.25-8.14 (s(vbr.), o-H of C.sub.6H.sub.4NMe.sub.2),
6.55 (d, .sup.3J.sub.HH=7.2 Hz, m-H of C.sub.6H.sub.4NMe.sub.2),
2.97 (s, N(CH.sub.3).sub.2), 2.63-2.61, 1.80-1.67, 1.43-1.41 and
1.21-1.17 (all m, P(C.sub.6 H.sub.11).sub.3). .sup.13C NMR
(CD.sub.2Cl.sub.2): .delta. 286.13 (s(br.); Ru.dbd.CH), 151.28 (s;
ipso-C of C.sub.6H.sub.4NMe.sub.2), 144.80, 134.85 and 110.50 (all
s; C.sub.6H.sub.4NMe.sub.2), 40.30 (s, N(CH.sub.3).sub.2, 32.54
(pseudo-t, J.sub.app=8.2Hz, ipso-C of P(C.sub.6H.sub.11).sub.3)
30.10 (s, m-C of P(C.sub.6H.sub.11).sub.3), 28.36 (m, o-C of
P(C.sub.6 H.sub.11).sub.3), 27.07 (s, p-C of
P(C.sub.6H.sub.11).sub.3. .sup.31P NMR (CD.sub.2Cl.sub.2); .delta.
34.94 (s, PCy.sub.3). Anal. Calcd. for
C.sub.45H.sub.77Cl.sub.2NP.sub.2 Ru: C, 62.41; H, 8.96; N, 1.62.
Found: C, 62.87; H, 9.04; N, 1.50.
Synthesis of
RuCl.sub.2(.dbd.CH-p-C.sub.6H.sub.4OMe)(PCy.sub.3).sub.2 (Complex
12)
[0089] Starting with
RuCl.sub.2(.dbd.CH-p-C.sub.6H.sub.4OMe)(PPh.sub.3).sub.2 (171 mg,
0.21 mmol) and tricyclohexylphosphine (130 mg, 0.46 mmol, 2.2 eq.),
RuCl.sub.2(.dbd.CH-p-C.sub.6H.sub.4OMe)(PCy.sub.3).sub.2 was
obtained as a dark-purple microcrystalline solid, in a technique
analogous to that used in synthesizing complex 10. Yield 152 mg
(85%). .sup.1H NMR (CD.sub.2 Cl.sub.2): .delta. 19.48 (s,
Ru.dbd.CH), 8.43 (s(br.), o-H of C.sub.6 H.sub.4 OMe), 6.82 (d,
J.sub.HH=8.6 Hz, m=H of C.sub.6 H.sub.4 OMe), 3.82 (s, OCH.sub.3),
2.64-2.59, 1.78-1.68, 1.46-1.39 and 1.26-1.15 (all m, P(C.sub.6
H.sub.11).sub.3, .sup.13 C NMR (CD.sub.2 Cl.sub.2); .delta. 290.90
(s(br.), Ru.dbd.CH), 148.34 (s, ipso-C of C.sub.6H.sub.4OMe),
134.91 132.30 and 128.83 (all s, C.sub.6H.sub.4OMe), 55.81 (s,
OCH.sub.3), 32.51 (pseudo-t, J.sub.app=9.1 Hz, ipso-C of
P(C.sub.6H.sub.11).sub.3), 30.06 (s, m-C of
P(C.sub.6H.sub.11).sub.3), 28.28 (pseudo-t, J.sub.app=5.2 Hz, o-C
of P(C.sub.6H.sub.11).sub.3), 27.00 (s, p-C of
P(C.sub.6H.sub.11).sub.3). .sup.31P NMR (CD.sub.2 Cl.sub.2):
.delta. 35.83 (s, PCy.sub.3). Anal. Calcd. for C.sub.44
H.sub.74Cl.sub.2OP.sub.2Ru: C, 61.96; H, 8.74. Found: C, 62.36; H,
8.71.
Synthesis of
RuCl.sub.2(.dbd.CH-p-C.sub.6H.sub.4Me)(PCy.sub.3).sub.2 (Complex
13)
[0090] Starting with RuCl.sub.2(.dbd.CH-p-C.sub.6 H.sub.4
Me(PPh.sub.3).sub.2 (416 mg, 0.52 mmol) and tricyclohexylphosphine
(321 mg, 1.14 mmol, 2.2 eq.),
RuCl.sub.2(.dbd.CH-p-C.sub.6H.sub.4Me)(PCy.sub.3).sub.2 was
obtained as a bright-purple microcrystalline solid, in a technique
analogous to that used in synthesizing complex 10. Yield 385 mg
(88%). .sup.1H NMR(CD.sub.2Cl.sub.2): .delta. 19.80 (s, Ru.dbd.CH),
d, .sup.3J.sub.HH=7.6 Hz, o-H of C.sub.6 H.sub.4 Me), 7.13 (d,
.sup.3J.sub.HH=7.6Hz, m-H of C.sub.6 H.sub.4 Me), 2.08 (s,
CH.sub.3), 2.62-2.58, 1.77-1.67, 1.43-1.40 and 1.22-1.17 (all m,
P(C.sub.6H.sub.11).sub.3). .sup.13C NMR (CD.sub.2Cl.sub.2): .delta.
293.86 (t, J.sub.PC=8.3 Hz, Ru.dbd.CH), 141.48 (s, ipso-C of
C.sub.6H.sub.4Me), 131.56 and 129.85 (both s, C.sub.6H.sub.4Me),
32.52 (pseudo-t, J.sub.app=9.2 Hz, ipso-C of
P(C.sub.6H.sub.11).sub.3), 30.07 (s, m-C of
P(C.sub.6H.sub.11).sub.3), 28.26 (pseudo-t, J.sub.app=4.1 Hz, o-C
of P(C.sub.6H.sub.11).sub.3), 27.00 (s, p-C of
P(C.sub.6H.sub.11).sub.3), 22.39 (s, CH.sub.3). .sup.31P NMR
(CD.sub.2Cl.sub.2): .delta. 36.09 (s, PCy.sub.3). Anal. Calcd. for
C.sub.44H.sub.74Cl.sub.2P.sub.2Ru: C, 63.14; H, 8.91. Found: C,
63.29; H 8.99.
Synthesis of RuCl.sub.2 (.dbd.CH-p-C.sub.6 H.sub.4
F)(PCy.sub.3).sub.2 (Complex 14)
[0091] Starting with RuCl.sub.2
(.dbd.CH-p-C.sub.6H.sub.4F)(PPh.sub.3).sub.2 (672 mg, 0.84 mmol)
and tricyclohexylphosphine (515 mg, 1.84 mmol, 2.2 eq.),
RuCl.sub.2(.dbd.CH-p-C.sub.6H.sub.4F)(PCy.sub.3).sub.2 was obtained
as a purple microcrystalline solid, in a technique analogous to
that used in synthesizing complex 10. Yield, 583 mg (83%). .sup.1H
NMR (CD.sub.2Cl.sub.2): .delta. 19.86 (s, Ru.dbd.CH), 8.52-8.50
(s(br.), o-H of C.sub.6H.sub.4F), 7.00 (dd,
.sup.3J.sub.HH=.sup.3J.sub.HF=8.8 Hz, m-H of C.sub.6H.sub.4F),
2.63-2.59, 1.77-1.68, 1.47''1.40 and 1.26-1.17 (all m,
P(C.sub.6H.sub.11).sub.3). .sup.13C NMR(CD.sub.2Cl.sub.2): .delta.
291.52 (t, J.sub.PC=8.6 HZ, Ru.dbd.CH), 162.10 (d, J.sub.CF=254.3
Hz, p-C of C.sub.6H.sub.4F), 150.57 (s, ipso-C of C.sub.6H.sub.4F),
134.10 (d, J.sub.CF=8.9 Hz, o-C of C.sub.6H.sub.4F), 116.00 (d,
.sub.jCF=21.3 Hz, m-C of C.sub.6H.sub.4F), 32.49 (pseudo-t,
J.sub.app=9.3 Hz, ipso-C of P(C.sub.6H.sub.11).sub.3), 30.05 (s,
m-C of P(C.sub.6H.sub.11).sub.3), 28.22 (pseudo-t, J.sub.app=5.2
Hz, o-C of P(C.sub.6H.sub.11).sub.3), 26.94 (s, p-C of
P(C.sub.6H.sub.11).sub.3. .sup.31P NMR(CD.sub.2Cl.sub.2): .delta.
36.60 (s, PCy.sub.3). .sup.19F NMR(CD.sub.2Cl.sub.2): .delta. 45.47
(s, C.sub.6H.sub.4F). Anal. Calcd. for
C.sub.43H.sub.71Cl.sub.2FP.sub.2 Ru: C, 61.41; H, 8.51. Found: C,
61.32; H, 8.59.
Synthesis of
RuCl.sub.2(.dbd.CH-p-C.sub.6H.sub.4Cl)(PCy.sub.3).sub.2 (Complex
15)
[0092] Starting with RuCl.sub.2 (.dbd.CH-p-C.sub.6 H.sub.4
Cl)(PPh.sub.3).sub.2 (543 mg, 0.66 mmol) and tricyclohexylphosphine
(408 mg, 1.45 mmol, 2.2 eq.), RuCl.sub.2
(.dbd.CH-p-C.sub.6H.sub.4Cl)(PCy.sub.3).sub.2 was obtained as a
purple microcrystalline solid in a technique analogous to that used
in synthesizing complex 10. Yield 493 mg (87%). .sup.1H
NMR(CD.sub.2Cl.sub.2): .delta. 19.98 (s, Ru.dbd.CH), 8.43 (d,
.sup.3J.sub.HH=8.7 Hz, o-H of C.sub.4H.sub.4Cl), 7.29 (d,
.sup.3J.sub.HH=8.7 Hz, m-H of C.sub.6H.sub.4Cl), 2.63-2.58,
1.76-1.68, 1.46-1.41 and 1.25-1;17 (all m, P(C.sub.6
H.sub.11).sub.3). .sup.13C NMR(CD.sub.2Cl.sub.2): .delta. 291.52
(t, J.sub.PC=8.0 HZ, Ru.dbd.CH), 151.81 (s, ipso-C of
C.sub.6H.sub.4Cl), 134.64 (s, p-C of C.sub.6H.sub.4Cl), 132.56 and
129.51 (both s, o-C and m-C of C.sub.6H.sub.4Cl), 32.51 (pseudo-t,
J.sub.app=8.9 Hz, ipso-C of P(C.sub.6H.sub.11).sub.3), 30.06 (s,
m-C of P(C.sub.6H.sub.11).sub.3), 28.22 (pseudo-t, J.sub.app=5.2
Hz, o-C of P(C.sub.6H.sub.11).sub.3), 26.96 (s, p-C of
P(C.sub.6H.sub.11).sub.3). .sup.31P NMR(CD.sub.2 Cl.sub.2): .delta.
36.81 (s, PCy.sub.3) Anal. Calcd. for
C.sub.43H.sub.71Cl.sub.2FP.sub.2Ru: C, 60.24; H, 8.35. Found: C,
60.22; H, 8.45.
Synthesis of
RuCl.sub.2(.dbd.CH-p-C.sub.6H.sub.4NO.sub.2)(PCy.sub.3).sub.2
(Complex 16)
[0093] Starting with
RuCl.sub.2(.dbd.CH-p-C.sub.6H.sub.4NO.sub.2)(PPh.sub.3).sub.2 (609
mg, 0.73 mmol) and tricyclohexylphosphine (452 mg, 1.61 mmol, 2.2
eq.), RuCl.sub.2(.dbd.CH-p-C.sub.6H.sub.4NO.sub.2)(PCy.sub.3).sub.2
was obtained, in a procedure analogous to that in example 11, as a
red-purple microcrystalline solid. Yield 527 mg (83%). .sup.1H
NMR(CD.sub.2Cl.sub.2): .delta. 20.71 (s, Ru.dbd.CH), 8.64 (d,
.sup.3J.sub.HH=8.4 Hz, o-H of C.sub.6H.sub.4NO.sub.2), 8.13 (d,
.sup.3J.sub.HH=8.4 Hz, m-H of C.sub.6H.sub.4 NO.sub.2), 2.63-2.58,
1.73-1.68, 1.47-1.40 and 1.26-1.17 (all m, P(C.sub.6
H.sub.11).sub.3). .sup.13C NMR (CD.sub.2 Cl.sub.2) .delta. 289.07
(t, J.sub.PC=7.6 Hz, Ru.dbd.CH), 155.93 (s, ipso-C of C.sub.6
H.sub.4 NO.sub.2), 145.34 (s, p-C of C.sub.6 H.sub.4 NO.sub.2),
131.22 and 125.06 (both s, o-C and m-C of C.sub.6H.sub.4NO.sub.2),
32.57 (pseudo-t, J.sub.app=9.2 Hz, ipso-C of
P(C.sub.6H.sub.11).sub.3), 30.05 (s, m-C of
P(C.sub.6H.sub.11).sub.3), 28.16 (pseudo-t, J.sub.app=4.1 Hz, o-C
of P(C.sub.6H.sub.11).sub.3). .sup.31P NMR(CD.sub.2Cl.sub.2):
.delta. 38.11 (s, PCy.sub.3). Anal. Calcd. for
C.sub.43H.sub.71Cl.sub.2NO.sub.2 P.sub.2 Ru: C, 59.50; H, 8.25; N,
1.61. Found: C, 59.18; H, 8.25; N, 1.49.
One-Pot Synthesis of RuCl.sub.2(.dbd.CHPh)(PCp.sub.3).sub.2
(Complex 17)
[0094] Complex 17 is obtained in analogy to complex 10 as a purple
microcrystalline solid, using RuCl.sub.2(PPh.sub.3).sub.3 (4.00 g,
4.17 mmol), phenyldiazomethane (986 mg, 8.35 mmol, 2.0 eq.), and
tricyclopentylphosphine (2.19 g, 9.18 mmol, 2.2. eq.). Due to the
better solubility of 17, only methanol is used for the washings.
Yield 2.83 g (92%). .sup.1H NMR (CD.sub.2Cl.sub.2): .delta. 20.20
(s, Ru.dbd.CH), 8.47 (d, .sup.3J.sub.HH=7.5 Hz, o-H of C.sub.6
H.sub.5), 7.63 (t, .sup.3J.sub.HH=7.5 Hz, p-H of C.sub.6H.sub.5),
7.36 (t, .sup.3J.sub.HH=7.5 Hz, m-H of C.sub.6H.sub.5), 2.68-2.62,
1.81-1.77, 1.62-1.52 and 1.49-1.44 (all m,
P(C.sub.5H.sub.8).sub.3). .sup.13C NMR (CD.sub.2Cl.sub.2): .delta.
300.52 (t, J.sub.PC=7.6 Hz, Ru.dbd.CH), 153.38 (s, ipso-C of
C.sub.6H.sub.5), 130.99, 129.80 and 129.53 (all s, C.sub.6 H.sub.5)
35.54 (pseudo-t, J.sub.app=11.2 Hz, ipso-C of
P(C.sub.5H.sub.9).sub.3) 29.99 and 26.39 (both s,
P(C.sub.5H.sub.9).sub.3). .sup.31P NMR (CD.sub.2 Cl.sub.2): .delta.
29.96 (s, PCp.sub.3). Anal. Calcd. for
C.sub.37H.sub.60Cl.sub.2P.sub.2Ru: 60.15; H, 8.19. Found: C, 60.39;
H, 8.21.
One-Pot Synthesis of RuCl.sub.2(.dbd.CHPh)(PiPr.sub.3).sub.2
(Complex 18)
[0095] Complex 18 is obtained in analogy to complex 17 as a purple
microcrystalline solid, using RuCl.sub.2(PPh.sub.3).sub.3 (4.00 g,
4.17 mmol), phenyldiazomethane (986 mg, 8.35 mmol, 2.0 eq.), and
triisopropylphosphine (1.79 mL, 9.18 mmol, 2.2. eq.). Yield 2.26 g
(93%). .sup.1H NMR (CD.sub.2Cl.sub.2): .delta. 220.10 (s,
Ru.dbd.CH), 8.52 (d, .sup.3J.sub.HH=7.6 Hz, o-H of C.sub.6 H.sub.5,
7.36 (t, J.sub.HH=7.6 Hz, p-H of C.sub.6H.sub.5), 7.17 (t,
.sup.3J.sub.HH=7.6 Hz, m-H of C.sub.6 H.sub.5), 2.88-2.85, (m,
PCHCH.sub.3); 1.19 (dvt, N=13.6 Hz, PCHCH.sub.3). .sup.13C NMR
(CD.sub.2Cl.sub.2): .delta. 296.84 (s(br.), Ru.dbd.CH), 152.81 (s,
ipso-C of C.sub.6H.sub.5), 131.37, 129.54 and 129.20 (all s,
C.sub.6H.sub.5) 22.99 (vt, N=.sup.2 J.sub.PC+.sup.4 J.sub.PC=18.9
Hz, PCHCH.sub.3), 19.71 (s, PCHCH.sub.3). .sup.31P NMR
(CD.sub.2Cl.sub.2): .delta. 45.63 (s, PiPr.sub.3). Anal. Calcd. for
C.sub.25H.sub.48Cl.sub.2P.sub.2Ru: C, 51.54; H, 8.31. Found: C,
51.69; H, 8.19.
Synthesis of RuCl.sub.2(.dbd.CH.sub.2)(PCy.sub.3).sub.2 (Complex
19)
[0096] A solution of RuCl.sub.2(.dbd.CHPh)(PCy.sub.3).sub.2 (821
mg, 1.00 mmol) in CH.sub.2Cl.sub.2 (15 mL) was stirred under an
atmosphere of ethylene for 15 min at RT. The solvent was removed
under vacuum, the residue repeatedly washed with acetone or pentane
(5 mL) and dried under vacuum for several hours. A burgundy
microcrystalline solid was obtained. Yield 745 mg (quant.). .sup.1H
NMR (CD.sub.2Cl.sub.2): .delta. 18.94 (s, Ru.dbd.CH.sub.2),
2.50-2.44, 1.81-1.70, 1.49-1.43 and 1.25-1.23 (all m,
P(C.sub.6H.sub.11).sub.3). .sup.13C NMR (CD.sub.2Cl.sub.2): .delta.
294.71 (t, J.sub.PC=7.6 Hz, J.sub.CH=164.0 Hz (gated decoupled),
Ru.dbd.CH), 31.051 pseudo-t, J.sub.app=9.6 Hz, ipso-C of
P(C.sub.6H.sub.11)3), 29.58 (s, m-C of P(C.sub.6H.sub.11).sub.3),
28.20 (pseudo-t, J.sub.app=5.3 Hz, o-C of
P(C.sub.6H.sub.11).sub.3), 26.94 (s, p-C of
P(C.sub.6H.sub.11).sub.3) .sup.31P NMR (CD.sub.2 Cl.sub.2): .delta.
43.74 (s, PCy.sub.3). Anal. Calcd. for C.sub.37
H.sub.68Cl.sub.2P.sub.2Ru: C, 59.50; H, 9.18. Found: C, 59.42; H,
9.29.
Synthesis of RuCl.sub.2(.dbd.CHMe)(PCy.sub.3).sub.2 (Complex
20)
[0097] In a procedure analogous to that used in synthesizing
complex 19, RuCl.sub.2(.dbd.CHMe)(PCy.sub.3).sub.2 was obtained as
a red-purple microcrystalline solid, using
RuCl.sub.2(.dbd.CHPh)(PCy.sub.3).sub.2 (763 mg, 0.93 mmol) and
propylene (or 2-butene) as starting materials. Yield 691 mg (98%).
.sup.1H NMR (CD.sub.2Cl.sub.2): .delta. 19.26 (q,
.sup.3J.sub.HH=5.1, Hz, Ru.dbd.CH), 2.57 (d, .sup.3J.sub.HH=5.1 Hz,
CH.sub.3), 2.59-2.53, 1.87-1.79, 1.57-1.50 and 1.28-1.23 (all m,
P(C.sub.6H.sub.11).sub.3). .sup.13C NMR (CD.sub.2Cl.sub.2): .delta.
316.32 (t, J.sub.PC=7.6 Hz, Ru.dbd.CH), 49.15 (s, CH.sub.3), 32.37
(pseudo-t, J.sub.app=9.4 Hz, ipso-C of P(C.sub.6H.sub.11).sub.3),
29.87 (s, m-C of P(C.sub.6H.sub.11).sub.3), 28.22 (pseudo-t,
J.sub.app=5.0 Hz, o-C of P(C.sub.6H.sub.11).sub.3), 26.94 (s, p-C
of P(C.sub.6H.sub.11).sub.3). .sup.31P NMR (CD.sub.2Cl.sub.2):
.delta. 35.54 (s, PCy.sub.3). Anal. Calcd. for
C.sub.38H.sub.70Cl.sub.2P.sub.2Ru: C, 59.58; H, 9.27. Found: C,
59.91; H, 9.33.
Synthesis of RuCl.sub.2(.dbd.CHEt)(PCy.sub.3).sub.2 (Complex
21)
[0098] In a procedure analogous to that used in synthesizing
complex 19, RuCl.sub.2(.dbd.CHEt)(PCy.sub.3).sub.2 was obtained as
a red-purple microcrystalline solid, using
RuCl.sub.2(.dbd.CHPh)(PCy.sub.3).sub.2 and a tenfold excess of
1-butene (or cis-3-hexene) as starting materials. Yield 616 mg
(97%). .sup.1H NMR (CD.sub.2Cl.sub.2): .delta. 19.12 (t,
.sup.3J.sub.HH=5.0 Hz, Ru.dbd.CH), 2.79 (dq, .sup.3J.sub.HH=5.0,
.sup.3J.sub.HH'=7.1 Hz, CH.sub.2 CH.sub.3), 2.55-2.49, 1.84-1.81,
1.54-1.47 and 1.26-1.23 (all m, P(C.sub.6H.sub.11).sub.3), 1.35 (t,
3J.sub.HH'=7.1 Hz, CH.sub.2CH.sub.3). .sup.13C NMR
(CD.sub.2Cl.sub.2): .delta. 322.59 (t, J.sub.PC=9.3 Hz, Ru.dbd.CH),
53.48 (s, CH.sub.2CH.sub.3), 32.20 (pseudo-t, J.sub.app=8.9 Hz,
ipso-C of P(C.sub.6H.sub.11).sub.3), 29.85 (s, m-C of
P(C.sub.6H.sub.11).sub.3, 29.57 (s, CH.sub.2CH.sub.3), 28.22
(pseudo-t, J.sub.app=4.6 Hz, O-C of P(C.sub.6H.sub.11).sub.3),
26.88 (s, p-C of P(C.sub.6H.sub.11).sub.3). .sup.31P NMR
(CD.sub.2Cl.sub.2): .delta. 36.39 (s, PCy.sub.3). Anal. Calcd. for
C.sub.39H.sub.72Cl.sub.2P.sub.2Ru:, C, 60.45; H, 9.37. Found: C,
60.56; H, 9.30.
Synthesis of RuCl.sub.2(.dbd.CH-n-Bu)(PCy.sub.3).sub.2 (Complex
22)
[0099] In a procedure analogous to that used in synthesizing
complex 19, RuCl.sub.2(.dbd.CH-n-Bu)(PCy.sub.3).sub.2 was obtained
as a red-purple microcrystalline solid, using
RuCl.sub.2(.dbd.CHPh)(PCy.sub.3).sub.2 (354 mg, 0.43 mmol) and
1-hexene (538 .mu.L, 4.30 mmol, 10 eq.) as starting materials.
Yield 328 mg (95%). .sup.1H NMR (CD.sub.2Cl.sub.2); .delta. 19.24
(t, 3 J.sub.HH=5.1 Hz, Ru.dbd.CH), 2.74 (dt, .sup.3J.sub.HH=5.1,
.sup.3J.sub.HH'=5.2 Hz, (CHCH.sub.2), 2.56-2.47, 1.82-1.78,
1.70-1.68, 1.54-1.43, 1.26-1.22 and 0.95-0.86 (all m, CH.sub.2
CH.sub.2 CH.sub.3 and P(C.sub.6 H.sub.11).sub.3). .sup.13C NMR
(CD.sub.2Cl.sub.2): .delta. 321.13 (t, J.sub.PC=7.6 Hz, Ru.dbd.CH),
58.85 (s, CHCH.sub.2) 32.25 (pseudo-t, J.sub.app=9.4 Hz, ipso-C of
P(C.sub.6H.sub.11).sub.3), 29.90 (s, m-C of
P(C.sub.8H.sub.11).sub.3), 28.23 (pseudo-t, J.sub.app=5.3 Hz, O-C
of P(C.sub.6H.sub.11).sub.3, 26.91 (s, p-C of
P(C.sub.6H.sub.11).sub.3), 30.53, 22.94 and 14.06 (all s,
CH.sub.2CH.sub.2CH.sub.3). .sup.31P NMR (CD.sub.2Cl.sub.2): .delta.
36.05 (s, PCy.sub.3). Anal. Calcd. for
C.sub.41H.sub.76Cl.sub.2P.sub.2Ru: C, 61.32; H, 9.54. Found: C,
61.51; H, 9.71.
Synthesis of RuCl.sub.2(.dbd.CHCH.dbd.CH.sub.2)(PCy.sub.3).sub.2
(Complex 23)
[0100] 1,3-butadiene is slowly bubbled into a solution of complex
10 (703 mg, 0.85 mmol) in CH.sub.2Cl.sub.2 (15 mL) for 20 seconds
at -20.degree. C. While the solution is allowed to warm to RT
within 10 min, a color change from purple to orange-brown is
observed. The solvent was removed under vacuum, the residue
repeatedly washed with acetone or pentane (5 mL) and dried under
vacuum for several hours. A red-purple microcrystalline solid was
obtained. Yield 627 mg (95%). .sup.1H NMR (CD.sub.2Cl.sub.2):
.delta. 19.06 (d, .sup.3J.sub.HH=10.5 Hz, Ru.dbd.CH), 8.11 (ddd,
.sup.3J.sub.HH 10.5, .sup.3J.sub.HH cis=9.3, .sup.3J.sub.HH
trans=16.8 Hz, CH.dbd.CH.sub.2), 6.25 (d, .sup.3J.sub.HH cis=9.3,
H.sup.cis of CH.dbd.CH.sub.2), 6.01 (d, .sup.3J.sub.HH trans=9.3,
H.sup.trans of CH.dbd.CH.sub.2), 2.59-2.53, 1.83-1.78, 1.52-1.47
and 1.25-1.21 (all m, P(C.sub.6H.sub.11).sub.3). .sup.13C NMR
(CD.sub.2Cl.sub.2): .delta. 296.00 (t, J.sub.PC 7.6 Hz. Ru.dbd.CH),
153.61 (s, CH.dbd.CH.sub.2), 115.93 (s, CH.dbd.CH.sub.2), 32.32
(pseudo-t, J.sub.app=8.9 Hz, ipso-C of P(C.sub.6H.sub.11).sub.3),
29.82 (s, m-C of P(C.sub.6H.sub.11).sub.3), 28.15 (pseudo-t,
J.sub.app=5.1 Hz, O-C of P(C.sub.6H.sub.11).sub.3), 26.91 (s, p-C
of P(C.sub.6H.sub.11).sub.3). .sup.31P NMR (CD.sub.2Cl.sub.2):
.delta. 36.17 (s, PCy.sub.3). Anal. Calcd. for
C.sub.38H.sub.70Cl.sub.2P.sub.2Ru: C, 60.61; H, 9.13. Found: C,
60.79; H, 9.30.
Synthesis of RuCl.sub.2(.dbd.C.dbd.CH.sub.2)(PCy.sub.3).sub.2
(Complex 24)
[0101] In a procedure analogous to that used in synthesizing
complex, 23, RuCl.sub.2(.dbd.C.dbd.CH.sub.2)(PCy.sub.3).sub.2 was
obtained as a tan microcrystalline solid, using complex 10 (413 mg,
0.50 mmol) and 1,2-propadiene as starting materials. Yield 373 mg
(98%). .sup.1H NMR (CD.sub.2Cl.sub.2): .delta. 3.63 (s,
Ru.dbd.C.dbd.CH.sub.2), 2.71-2.64, 2.05-2.01, 1.81-1.53 and
1.32-1.23 (all m, P(C.sub.6H.sub.11).sub.3. .sup.13C NMR
(CD.sub.2Cl.sub.2): .delta. 327.41 (t, J.sub.PC=17.2 Hz,
Ru.dbd.C.dbd.CH.sub.2), 99.34 (s, Ru.dbd.C.dbd.CH.sub.2), 33.30
(pseudo=t, J.sub.app=8.9 Hz, ipso-C of P(C.sub.6H.sub.11).sub.3),
30.41 (s, m-C of P(C.sub.6H.sub.11).sub.3), 28.32 (pseudo-t,
J.sub.app=5.0 Hz, o-C of P(C.sub.6H.sub.11).sub.3), 27.02 (s, p-C
of P(C.sub.6H.sub.11).sub.3). .sup.31P NMR (CD.sub.2Cl.sub.2):
.delta. 35.36 (s, PCy.sub.3). Anal. Calcd. for
C.sub.38H.sub.68Cl.sub.2P.sub.2Ru: C, 60.14; H, 9.03. Found: C,
60.29; H, 8.91.
Synthesis of RuCl.sub.2(.dbd.CHCH.sub.2 OAc)(PCy.sub.3).sub.2
(Complex 25)
[0102] A solution of complex 10 (423 mg, 0.51 mmol) in
CH.sub.2Cl.sub.2 (10 mL) was treated with allyl acetate (555 .mu.L,
5.10 mmol, 10 eq.) at -20.degree. C. While the solution warmed to
RT within 10 min, a color change from purple to orange-brown was
observed. The solvent was removed under vacuum, the residue
repeatedly washed with ice-cold methanol (5 mL portions) and dried
under vacuum for several hours. A purple microcrystalline solid,
RuCl.sub.2 (.dbd.CHCH.sub.2 OAc)(PCy.sub.3).sub.2, was obtained.
Yield 342 mg (83%). .sup.1H NMR (CD.sub.2Cl.sub.2): .delta. 18.90
(t, .sup.3J.sub.HH=4.2 Hz, Ru.dbd.CH), 4.77 (d, .sup.3J.sub.HH=3.6
Hz, CH.sub.2OAc), 2.09 (s, C(O)CH.sub.3), 2.53-2.47, 1.81-1.70,
1.59-1.53 and 1.26-1.22, (all m, P(C.sub.6 H.sub.11).sub.3).
.sup.13C NMR (CD.sub.2Cl.sub.2): .delta. 305.76 (t, J.sub.PC=7.6
Hz, Ru.dbd.C), 170.41 (s. C(O)CH.sub.3), 83.19 (s, CH.sub.2OAc),
32.59 (pseudo-t, J.sub.app=8.6 Hz, ipso-C of
P(C.sub.6H.sub.11).sub.3), 29.94 (s, m-C of
P(C.sub.6H.sub.11).sub.3), 28.23 (m, o-C of
P(C.sub.6H.sub.11).sub.3), 26.91 (s, p-C of
P(C.sub.6H.sub.11).sub.3), 20.91 (s, C(O)CH.sub.3). .sup.31P NMR
(CD.sub.2 Cl.sub.2): .delta. 36.66 (s, PCy.sub.3). Anal. Calcd. for
C.sub.39H.sub.72Cl20.sub.2P.sub.2Ru: C, 58.05; H, 8.99. Found: C,
58.13; H, 9.07.
Synthesis of RuCl.sub.2(.dbd.CHCH.sub.2Cl)(PCy.sub.3).sub.2
(Complex 26)
[0103] In a procedure analogous to that used in synthesizing
complex 25 RuCl.sub.2(.dbd.CHCH.sub.2Cl)(PCy.sub.3).sub.2 was
obtained as a purple microcrystalline solid using complex 10 (583
mg, 0.71 mmol) and allyl chloride (577 .mu.L, 7.08 mmol, 10 eq.) as
starting materials. Yield 552 mg (80%). .sup.1H
NMR(CD.sub.2Cl.sub.2): .delta. 18.74 (t, .sup.3J.sub.HH=4.5 Hz,
Ru.dbd.CH), 4.43(d, .sup.3J.sub.HH=4.8 Hz, CH.sub.2Cl), 2.55-2.50,
1.81-1.70, 1.59-1.52 and 1.27-1.23 (all m, P(C.sub.6
H.sub.11).sub.3). .sup.13C NMR(CD.sub.2Cl.sub.2): .delta. 303.00
(t, J.sub.PC=7.8 Hz, Ru.dbd.C), 63.23 (s, CH.sub.2Cl),
32.05(pseudo-t, J.sub.app=8.8 Hz, ipso-C of P(C.sub.6H.sub.11)3),
29.50(s, m-C of P(C.sub.6 H.sub.11)3), 27.81(pseudo-t,
J.sub.app=5.2 Hz, o-C of P(C.sub.6 H.sub.11).sub.3), 26.56 (s, p-C
of P(C.sub.6 H.sub.11).sub.3). .sup.31P NMR(CD.sub.2Cl.sub.2):
.delta. 37.36 (s, PCy.sub.3). Anal. Calcd. for
C.sub.38H.sub.69Cl.sub.3P.sub.2Ru: C, 57.39; H. 8.74. Found: C,
57.55; H, 8.81.
Synthesis of RuCl.sub.2(.dbd.CH(CH.sub.2).sub.3
OH)(PCy.sub.3).sub.2 (Complex 27)
[0104] In a procedure analogous to that used in synthesizing
complex 25, RuCl.sub.2(.dbd.CH(CH.sub.2).sub.3OH)(PCy.sub.3).sub.2
was obtained as a purple microcrystalline solid, using complex 10
(617 mg, 0.82 mmol) and 4pentene-1-ol (823 .mu.L, 8.2 mmol, 10 eq.)
as starting materials. Yield 459 mg (76%). .sup.1H
NMR(CD.sub.2Cl.sub.2): .delta. 19.20 (t, .sup.3J.sub.HH=4.6 Hz,
Ru.dbd.CH, 5.46(s(br.), OH), 2.82-2.78, 2.06-2.01 and 1.62-1.58
(all m, CH.sub.2CH.sub.2CH.sub.2 OH), 2.55-2.51, 1.84-1.81,
1.55-1.52 and 1.26-1.23 (all m, P(C.sub.6H.sub.11).sub.3). .sup.13C
NMR(CD.sub.2 Cl.sub.2): .delta. 305.66 5, J.sub.PC=7.3 Hz,
Ru.dbd.C, 62.66 (s, CH.sub.2OH), 33.01 and 30.08 (both s,
CH.sub.2CH.sub.2) 32.32(pseudo-t, J.sub.app=8.5 Hz, ipso-C of
P(C.sub.6H.sub.11).sub.3), 29.94 (s, m-C of P(C.sub.6
H.sub.11).sub.3), 28.28. (pseudo-t, J.sub.app=5.3 Hz, o-C of
P(C.sub.6H.sub.11).sub.3), 26.91 (s, p-C of
P(C.sub.6H.sub.11).sub.3). .sup.31P NMR(CD.sub.2Cl.sub.2): .delta.
37.06 (s, PCy.sub.3). Anal. Calcd. for
C.sub.40H.sub.74Cl.sub.2P.sub.2ORu: C, 59.69; H, 9.27. Found: C,
59.51; H. 9.09.
ROMP of Norbornene With Complexes 3-9 As Catalysts
[0105] Norbornene (59 mg, 0.63 mmol) was dissolved in
CH.sub.2Cl.sub.2 (0.7 mL) and treated with solutions of complexes
3-9 (6.25 .mu.mol) in CH.sub.2Cl.sub.2 (0.3 mL) at RT. The reaction
mixtures became viscous within 3-5 min and the color changed from
brown-green to orange. The solutions were stirred at RT for 1 hour,
then exposed to air and treated with CH.sub.2Cl.sub.2 (2 mL)
containing traces of 2,6-di-tert-butyl-4-methylphenol and ethyl
vinyl ether. The resulting green solutions were stirred for 20 min
and, after filtration through short columns of silica gel,
precipitated into vigorously stirred methanol. White, tacky
polymers were obtained that were isolated, washed several times
with methanol and dried under vacuum. Yields 95-99%, .apprxeq.90%
trans, M.sub.n=31.5-42.3 kg/mol, PDI (toluene): 1.04-1.10.
Determination of Initiation And Propagation Rates In ROMP of
Norbornene With Complexes 3-9
[0106] 1.25.times.10.sup.-5 mol of catalysts based on complexes 3-9
were weighed into NMR tubes and dissolved in benzene-d.sub.6 (0.3
mL). Ferrocene stock solution in benzene-d.sub.6 (20 .mu.L) was
added as an internal standard. These mixtures were treated with
solutions of norbornene (23.5 mg, 0.25 mmol, 20 eq.) in
benzene-d.sub.6 (250 .mu.L). A .sup.1H NMR-routine was started
immediately, taking 60 spectra within 40 min, then 200 spectra
within 5 hour. The initiation rate constants (k.sub.i) were
determined by integration of H.sub..alpha. resonances of the
initiating and propagating species. The propagation rate constants
(k.sub.p) were determined by monitoring the decrease of monomer
concentration versus the internal standards. The results are given
in Table III (above).
Reaction of Complex 10 With 3-methyl-1-butene And
3,3-dimethyl-1-butane
[0107] In individual NMR-tubes, a solution of complex 10 (5.0 mg,
6.1 .mu.mol) in methylene chloride-d.sub.2 (0.5 mL) was treated
with 10 equiv. 3-methyl-1-butene and 3,3-dimethyl-1-butene (61.0
.mu.mol), respectively. Whereas with the latter reactant, no
reaction was observed within 12 hours, a gradual (within 5 min)
color change from red-purple to orange indicates that complex 10
undergoes a reaction with 3-methyl-i-butene. Resonances in the
.sup.1H NMR at .delta. 18.96 (d, .sup.3J.sub.HH=7.5 Hz,
Ru.dbd.CHiPr), 2.27 (m, CHCH.sub.3) and 1.01 (d, .sup.3J.sub.HH=7.2
Hz, CHCH.sub.3) may be attributed to the formation of RuCl.sub.2
(.dbd.CH-i-Pr)(PCy.sub.3).sub.2. However, the intensity of these
signals did not increase in the course of the reaction, and after
10 min, the corresponding resonances of complex 19 became
dominant.
ROMP of Cyclooctene And 1,5-cyclooctadiene With Complexes 10-16 As
Catalysts
[0108] Complexes 10-16 (6.0 .mu.mol) were individually dissolved in
CH.sub.2Cl.sub.2 (0.5 mL) and treated with neat cyclooctene or
1,5-cyclooctadiene (3.0 mmol, 500 eq.) at RT. Accompanied by a
color change from purple to orange, the reaction mixtures turned
viscous within 3-5 min. The solutions were stirred at RT for 2.5
hour and, upon exposure to air, treated with CH.sub.2Cl.sub.2 (5
mL) containing traces of 2,6-di-tert-butyl-4methylphenol and ethyl
vinyl ether. After 20 min, the viscous solutions were filtered
through short columns of silica gel and precipitated into
vigorously stirred methanol. The resulting polymers were isolated,
washed several times with methanol and dried under vacuum.
Cycloocteneamer (white tacky polymers): Yields 95-100%,
M.sub.n=111-211 kg/mol, PDI (toluene): 1.51-1.63; polybutadiene:
(white glue-like polymers): Yields 96-99%, 56-68% cis, M.sub.n
57.9-63.2 kg/mol, PDI (toluene): 1.56-1.67.
Determination of Initiation Rate Constants In Acyclic Metathesis of
1-hexene With Complexes 10-16 As Catalysts
[0109] 6.05 .mu.mol of catalysts based on complexes 10-16 were
placed into NMR tubes and dissolved in methylene chloride-d.sub.2
(550 .mu.L). At 0.degree. C., 1-hexene (22.7 .mu.L, 0.18 mmol, 30
eq.) was added and a .sup.1H NMR-routine (at 0.degree. C.) was
started, taking 60 spectra within 40 min. The initiation rate
constants were determined by integration of the H.sub..alpha.
resonances of complexes 10-16 and 22. The results are given in
Table IV (above).
X-Ray Diffraction Study of
RuCl.sub.2(.dbd.CH-p-C.sub.6H.sub.4Cl)(PCy.sub.3).sub.2 (Complex
15)
[0110] A maroon prism of complex 15 was obtained by slow diffusion
of hexanes into a concentrated solution of complex 15 in methylene
chloride (0.5 mL) within 24 hours. A crystal of the size 0.2
mm.times.0.3 mm.times.0.5 mm was selected, oil-mounted on a glass
fiber and transferred to a Siemens P4 diffractometer equipped with
a modified LT-1 low temperature system. The determination of Laue
symmetry, crystal class, unit cell parameters, and the crystal's
orientation matrix were carried out according to standard
techniques. Low temperature (158 K) intensity data were collected
via a 2.theta.-.theta. scan technique with MO.sub.K.alpha.
radiation.
[0111] All 7782 data were corrected for absorption and for Lorentz
and polarization effects and placed on an approximately absolute
scale. Any reflection with I(net)<0 was assigned the value
|F.sub.0|=0. There were no systematic extinctions nor any
diffraction symmetry other than the Friedel condition. Refinement
of the model proved the centrosymmetric triclinic space group P1 to
be the correct choice.
[0112] All crystallographic calculations were carried out using
either the UCLA Crystallographic Computing Package or the SHELXTL
PLUS program. The analytical scattering factors for neutral atoms
were used throughout the analysis; both the real (.DELTA.f') and
imaginary (i.DELTA.f'') components of anomalous dispersion were
included. The quantity minimized during least-squares analysis was
.sigma.x(|F.sub.0|-|F.sub.c|.sup.2 where
w.sup.-1=.sigma..sup.2(|F.sub.0|)+0.0002(|F.sub.0|).sup.2. The
structure was solved by direct methods (SHELXTL) and refined by
full-matrix least-squares techniques. Hydrogen atoms were located
from a difference-Fourier map and included with isotropic
temperature parameters. Refinement of the model led to convergence
with R.sub.F=3.5%, R.sub.wF=3.6% and GOF=1.42 for 726 variables
refined against those 6411 data with
|F.sub.0|>3.0.sigma.(|F.sub.0|)). A final difference-Fourier map
yielded .rho.max=0.52 e.ANG..sup.-3.
* * * * *