throbber
PCI‘
`
`International Bureau
`WORLD INTELLECTUAL PROPERTY ORGANIZATION
`
`
`
`INTERNATIONAL APPLICATION PUBLISHED UNDER THE PATENT COOPERATION TREATY (PCT)
`
`
`(51) International Patent Classification 5 3
`
`C031?
`
`(11) International Publication Number:
`
`W0 93/20111
`
`(43) International Publication Date:
`
`14 October 1993 (14.10.93)
`
`if!
`
`(21) International Application Number:
`
`PCT/USQ3/03425
`
`(22) International Filing Date:
`
`5 April 1993 (05.04.93)
`
`(74) Agents: EVANS, Susan, B. et al.; E.I. du Pont de Ne-
`mours and Company, Legal/Patent Records Center,
`1007 Market Street, Wilmington, DE 19898 (US).
`
`(30) Priority data:
`07/863,606
`
`3 April 1992 (03.04.92)
`
`US
`
`(81) Designated States: JP, KR, European patent (AT, BE, CH,
`DE, DK, ES, FR, GB, GR, IE, IT, LU, MC, NL, PT,
`SE).
`
`(71) Applicants: E.I. DU PONT DE NEMOURS AND COM-
`PANY [US/US]; 1007 Market Street, Wilmington, DE Published
`19898 (US). CALIFORNIA INSTITUTE OF TECH-
`Without international search report and to be republished
`NOLOGY [US/US]; 1201 East California, Pasadena,
`upon receipt of that report.
`CA 91125 (US).
`
`
`
`(72) Inventors: GRUBBS, Robert, Howard ; 1700 Spruce Street,
`South Pasadena, CA 91030 (US). JOHNSON, Lynda,
`Kaye ; 601 Jones Ferry Road A3, Carrboro, NC 27510
`(US). NGUYEN, Sonbinh, Thebao ; 103 Mosher-Jorgen-
`sen House, Pasadena, CA 91125 (US).
`
`(54) Title: RUTHENIUM AND OSMIUM METAL CARBENE COMPLEXES FOR OLEFIN METATHESIS POLYMERI-
`ZATION
`
`(57) Abstract
`
`Processes for the synthesis of several new carbene compounds of ruthenium and osmium are provided. These novel com~
`plexes function as stable, well-defined catalysts for the metathesis polymerisation of cyclic olefins. .
`
`

`

`FOR THE PURPOSES OF INFORMATION ONLY
`
`Codes used to identify States party to the PCT on the front pages of pamphlets publishing international
`applications under the PCI‘.
`
`AT
`AU
`BB
`BE
`BF
`36
`BJ
`BR
`CA
`CF
`CO
`CH
`CI
`CM
`CS
`CZ
`DE
`DK
`ES
`FI
`
`Austria
`Australia
`Barbados
`Belgium
`Burkina Faso
`Bulgaria
`Benin
`BraziI
`Canada
`Central African Republic
`Congo
`Switzerland
`(.‘éle d‘lvoire
`(‘ameroon
`Czechoslovakia
`(Ewell Republic
`Germany
`Denmark
`Spain
`Finland
`
`Viet Nam in
`
`France
`Gabon
`United Kingdom
`Guinea
`Greece
`Hungary
`Ireland
`Italy
`Japan
`Democratic: People‘s Republic
`of Korea
`Republic of Korea
`Kazakhstan
`Liechtenslein
`Sri lanka
`Luxembourg
`Monaco
`Madagascar
`Mali 7
`Mongolia
`
`Mauritania
`Malawi
`Netherlands
`Norway
`New Zealand
`Poland
`Portugal
`Romania
`Russian Federation
`Sudan
`Sweden
`Slovak Republic
`Senegal
`Soviet Union
`Chad
`Togo
`Ukraine
`United States of America
`
`“I
`
`

`

`W0 93/l0] 1 l
`
`PCT/US93/03425
`
`TLE
`
`RUTHENIUM AND OSMIUM METAL CARBENE
`
`COMPLEXES FOR OLEFIN METATHESIS POLYMERIZATION
`
`BAQKQRQQND QF IHE INVENTIQN
`
`This invention relates to new ruthenium and osmium
`
`metal carbene complex compounds and their utility in an
`improved catalytic process for olefin metathesis
`
`polymerization.
`
`10
`
`During the past two decades, research efforts have
`
`enabled an in depth understanding of the olefin
`
`metathesis reaction as catalyzed by early transition
`metal complexes.
`In contrast,
`the nature of the
`
`15
`
`intermediates and the reaction mechanism for Group VIII
`transition metal catalysts has remained elusive.
`In
`
`the oxidation states and ligation of the
`particular,
`ruthenium and osmium metathesis intermediates are not
`
`known. Furthermore,
`
`the discrete ruthenium and osmium
`
`carbene complexes isolated to date do not exhibit
`
`20
`
`metathesis activity.
`
`Many ruthenium and osmium metal carbenes have been
`
`reported in the literature (for example, see Burrell, A.
`K., Clark, G. R., Rickard, C. E. F., Roper, W. R.,
`Wright, A. H., J. Chem. Soc., Dalton Trans., 1991,
`1, pp. 609-614).
`
`Issue
`
`'W
`
`The present invention involves a reaction of a
`
`ruthenium or osmium compound with either a cyclopropene
`or,a phosphorane to produce well-defined carbene
`
`compounds which can be called carbene complexes and
`which can catalyze the polymerization of cyclic olefin
`via ring—opening metathesis.
`
`25
`
`30
`
`The carbene compounds of the present invention are
`
`35
`
`the only Ru and Os carbene complexes known to date in
`which the metal is formally in the +2 oxidation state,
`
`

`

`wo 93/201 11
`
`'
`
`Pcr/US93/03425
`
`2
`
`has an electron count of 16, and is pentacoordinate.
`
`The compounds claimed herein are active catalysts for
`ring—opening metathesis polymerization ("ROMP"). Host
`
`metathesis catalysts presently known are poisoned by
`functional groups and are,
`therefore,
`incapable of
`
`catalyzing metathesis polymerization reactions in protic
`
`or aqueous solvent systems.
`
`the present invention pertains to compounds
`Thus,
`of the formula
`
`10
`
`15
`
`20
`
`25
`
`30
`
`X L
`\ l /
`/M=C\
`I
`L1
`
`X
`
`R1
`
`R
`
`I
`
`wherein:
`
`M is Os or Ru;
`
`R and R1 are independently selected from hydrogen;
`cz-czo alkenyl,
`cz—czo alkynyl, C1-C20 alkyl,
`
`aryl, C1-C20 carboxylate, Cl—Czo alkoxy, C2—C20
`
`alkenyloxy, C2-C20 alkynyloxy, aryloxy, C2-Czo
`alkoxycarbonyl, C1-C20 alkylthio, C1—C20
`alkylsulfonyl or C1—C20 alkylsulfinyl; each
`
`optionally subStituted with C1—C5 alkyl,
`
`halogen, C1-C5 alkoxy or with a phenyl group
`
`optionally substituted with halogen, C1—C5 alkyl
`
`or C1-C5 alkoxy;
`
`X and X1 are independently selected from any anionic
`ligand; and
`L and L1 are independently selected from any neutral
`electron donor.
`
`they can be
`In one embodiment of these compounds,
`in the form wherein Z, 3, or 4 of the moieties X, X1, L,
`and L1 can be taken together to form a chelating
`multidentate ligand.
`In one aspect of this embodiment,
`
`”M
`
`

`

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`PCI‘/US93/03425
`
`3
`
`X, L, and L1 can be taken together to form a
`
`cyclopentadienyl,
`
`indenyl, or fluorenyl moiety.
`
`The present invention also pertains to a method of
`
`preparing the aforementioned ruthenium and osmium
`
`compounds comprising reacting a compound of the formula
`(XX1MLnL1m)p,
`in the presence of solvent, with a
`
`cyclopropene of the formula
`
`R2
`
`R3
`
`10
`
`15
`
`20
`
`25
`
`30
`
`.
`wherein:
`M, X, X1, L, and L1 have the same meaning as
`
`indicated above;
`
`n and m are independently 0-4, provided n+m=2, 3 or
`4;
`
`p is an integer equal to or greater than 1; and
`R2 and R3 are independently selected from hydrogen;
`C1-C18 alkyl, C2-C13 alkenyl, C2-C18 alkynyl,
`C2-C13 alkoxycarbonyl, aryl, C1-C13 carbonylate,
`
`C1—C13 alkenyloxy, C2—C13 alkynyloxy, C1-C13
`
`alkoxy, aryloxy, C1-C18 alkylthio, C1—C13
`
`alkylsulfonyl or C1-C13 alkylsulfinyl; each
`
`optionally substituted with C1—C5 alkyl,
`
`halogen, C1-C5 alkoxy or with a phenyl group
`
`optionally substituted with halogen, C1-C5 alkyl
`
`or C1-C5 alkoxy.
`
`In one embodiment of the process, X, L, and L1 are
`
`taken together to form a moiety selected from the group
`'consisting of cyclopentadienyl,
`indenyl or fluorenyl,
`each optionally substituted with hydrogen; C2-Czo
`alkenyl, C2-C20 alkynyl, C1-C20 alkyl, aryl, C1-C20
`
`carboxylate, C1-C20 alkoxy, C2-C20 alkenyloxy, C2-C20
`
`

`

`W0 93/2011 1
`
`PCTIUS93/03425
`
`4
`
`alkynyloxy, aryloxy, C2—C20 alkoxycarbonyl, C1-C20
`alkylthio, C1-C20 alkylsulfonyl, C1—C20 alkylsulfinyl;
`each optionally substituted with C1-C5 alkyl, halogen,
`C1-C5 alkoxy or with a phenyl group optionally
`substituted with halogen, C1—C5 alkyl or C1-C5 alkoxy.
`A still further method of preparing the compounds
`of this invention comprises reacting compound of the
`formula (XXlMLnle)p in the presence of solvent with
`phosphorane of the formula
`
`10
`
`15
`
`20
`
`25
`
`R4
`\ /
`R5—P = C\
`R5//
`
`R.
`
`R1
`
`wherein:
`
`M, X, X1, L, L1, n, m, p, R, and R1 have the same
`
`meaning as indicated above; and
`R4, R5 and R6 are independently selected from aryl,
`C1-C5 alkyl, C1-Cs alkoxy or phenoxy, each
`optionally substituted with halogen, C1-C3
`alkyl, C1-C3 alkoxy, or with a phenyl group
`optionally substituted with halogen, C1-C5 alkyl
`~ or C1-C5 alkoxy.
`
`Another embodiment of the invention comprises
`preparing compounds of Formulae II and III
`
`Y ‘L
`\| /
`j/hd:::C;\
`I
`L1
`
`Y
`
`R1
`
`R
`
`II
`
`"A
`
`IIr
`
`

`

`W0 93/2011]
`
`PCT/US93/03425
`
`5
`
`L
`
`R1
`
`'Y\I /
`[/h4:=:CK\
`I
`L1
`
`X
`
`R
`
`III
`
`from compound of Formula I
`
`L
`
`I
`X
`\
`X1/ I
`
`R
`/ ,.
`h4==:C
`\R
`
`Ll
`
`I
`
`comprising reacting said compound of Formula I,
`
`in the
`
`presence of solvent, with compound of the formula MlY
`wherein:
`
`M, R, R1 X, X1, L, and L1 have the same meaning as
`indicated above, and wherein:
`
`(1) M1 is Li, Na or K, and Y is C1-C10 alkoxide or
`
`arylalkoxide each optionally substituted with
`
`C1—C10 alkyl or halogen, diaryloxide; or
`(2) M1 is Na or Ag, and y is c104, PF6, BF4, SbFe,
`
`halogen, B(aryl)4, C1-C10 alkyl sulfonate or
`
`aryl sulfonate.
`
`Another embodiment of the present
`
`invention is a
`
`method of preparing compounds of structures of Formulae
`IV and V
`
`I?
`X\§l
`
`hd:::C
`
`R1
`
`//
`
`X1/ I
`
`L1
`
`\
`
`IV
`
`10
`
`15
`
`20
`
`25
`
`‘9
`
`

`

`W0 93/201 1 l
`
`PCT/US93/03425
`
`6
`
`R1
`
`XL2
`\| /
`/M_\
`I
`L2
`
`X?
`
`R
`
`V
`
`from compound of Formula I
`
`L
`
`1%
`
`Xi\l /
`/M=C\
`l
`L1
`
`X1
`
`R
`
`I
`
`comprising reacting said compound I,
`solvent, with L2 wherein:
`
`in the presence of
`
`M, R, R1 X, and X1 have the same meaning as
`indicated above; and
`
`L, L1, and L2 are independently selected from any
`neutral electron donor.
`
`The compounds of Formulae II, III,
`
`IV, and V are
`
`5
`
`10
`
`15
`
`the scope of compounds of
`species of, i.e., fall within,
`Formula I.
`In other words, certain compounds of Formula
`
`20
`
`I are used to form by ligand exchange other compounds of
`
`Formula I.
`
`In this case, X and X1 in Formula I are
`
`25
`
`other than the Y in Formulae II and III that replaces X.
`Similarly, L and L1 in Formula I are other than the L2
`in Formulae IV and V.
`If any 2, 3, or 4 of X, X1, L,
`and L1 form a multidentate ligand of Formula I, only the
`remaining ligand moieties would be available for ligand
`replacement.
`
`

`

`W0 93/20] l l
`
`PCT/ US93/03425
`
`7
`
`in
`
`Still another embodiment of the present invention
`
`involves the use of compound I as a catalyst for
`
`polymerizing cyclic olefin. More specifically, this
`
`embodiment comprises metathesis polymerization of a
`
`polymerizable cyclic olefin in the presence of catalyst
`of the formula
`
`L
`XI\
`lhd=::C
`
`R
`
`/
`
`10
`
`15
`
`20
`
`25
`
`30
`
`in the presence of solvent, wherein:
`
`M, R, R1, X, X1, L and L1 have the same meaning as
`indicated above.
`
`The reference above to X, X1, L, and L1 having the
`
`same meaning as indicated above refers to these moieties
`
`individually and taken together to form a multidentate
`
`ligand as described above.
`
`QEIALLED_D§§§BLEELQE
`
`The ruthenium and osmium metal complexes of'the
`
`present invention are useful as catalysts in ring-
`
`opening metathesis polymerization, particularly in the
`
`living polymerization of strained cyclic olefins.
`
`Although all the criteria for a living polymer have not
`
`been completely established,
`
`the term living is used in
`
`the sense that the propagating moiety is stable and will
`
`continue to polymerize additional aliquots of monomer
`
`for a period after the original amount of monomer has
`
`been consumed. Aspects of this invention include the
`
`metal complex compounds, methods for their preparation,
`
`as well as their use as catalysts in the ROMP reaction.
`
`Uses for the resultant polymer are well documented in
`
`the book, Olefin Metathesis, by K. J. Ivin, Academic
`
`Press, Harcourt Brace Jovanovich Publishers (1983).
`
`

`

`WO 93/20111
`
`PCT/US93/03425
`
`8
`
`(XXlMLnle)p are either
`The intermediate compounds
`available commercially or can be prepared by standard
`known methods.
`
`10
`
`15
`
`20
`
`25
`
`30
`
`Schmidbaur, H.
`the following respective references.
`et al., Phosphorus and Sulfur, Vol. 18, pp. 167-170
`(1983); Carter, F. L., Frampton, V. L., Chemical
`Reviews, Vol. 64, No. 5
`(1964).
`
`In the compounds of Formula I:
`
`alkyl can include methyl, ethyl, n—propyl,
`i—propyl, or the several butyl, pentyl or hexyl isomers;
`alkenyl can include l-propenyl, 2-propenyl;
`3—propenyl and the different butenyl, pentenyl and
`hexenyl isomers, 1,3-hexadienyl and 2,4,6—heptatrienyl,
`and cycloalkenyl;
`
`(CH3)2C=CHCHZO,
`alkenyloxy can include H2C=CHCH20,
`(CH3)CH=CHCH20,
`(CH3)CH=C(CH3)CH20 and CH2=CHCH2CH20;
`alkynyl can include ethynyl,
`l—propynyl, 3-propynyl
`and the several butynyl, pentynyl and hexynyl isomers,
`2,7—octadiynyl and 2,5,8-decatriynyl;
`alkynyloxy can include HCECCHZO, CH3CECCH20 and
`CH3CECCH20CH20;
`
`alkylthio can include, methylthio, ethylthio, and
`the several propylthio, butylthio, pentylthio and
`hexylthio isomers;
`
`alkylsulfonyl can include CH3SOZ, CH3CH2502,
`CH3CH2CH2802,
`(CH3)2CH802 and the different
`
`butylsulfonyl, pentylsulfonyl and hexylsulfonyl isomers;
`alkylsulfinyl can include CH3SO, CH3CH280,
`CH3CH2CHZSO,
`(CH3)2CHSO and the different butylsulfinyl,
`‘pentylsulfinyl and hexylsulfinyl isomers;
`carboxylate can include CH3C02CH3CH2C02, C5H5C02,
`(C6H5)CH2C02;
`
`1"
`
`

`

`W0 93/201 1 l
`
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`
`PCI‘/ US93/03425
`
`9
`
`aryl can include phenyl, p-tolyl and
`
`p-fluorophenyl;
`
`4-3
`
`alkoxide can include methoxide,
`phenoxide;
`
`t—butoxide, and
`
`diketonates can include acetylacetonate and
`
`2,4-hexanedionate;
`
`sulfonate can include trifluoromethanesulfonate,
`tosylate, and mesylate;
`
`phosphine can include trimethylphosphine,
`triphenylphosphine, and methyldiphenylphosphine;
`phosphite can include trimethylphosphite,
`triphenylphosphite, and methyldiphenylphosphite;
`phosphinite can include triphenylphosphinite, and
`methyldiphenylphosphinite;
`
`arsine can include triphenylarsine and
`trimethylarsine;
`
`stibine can include triphenylstibine and
`trimethylstibine;
`
`10
`
`15
`
`20
`
`amine can include trimethylamine,
`dimethylamine;
`
`triethylamine and
`
`25
`
`3O
`
`ether can include (CH3)3CCH20CH2CH3, THF,
`(CH3)3COC(CH3)3, CH3OCH2CH20CH3, and CH3OC6H5;
`'
`thioether can include CH3SCH3, C6H58CH3,
`CH3OCH2CH28CH3, and tetrahydrothicphene;
`
`amide can include HC(=O)N(CH3)2 and
`
`(CH3)C(=O)N(CH3)2;
`
`sulfoxide can include CH3S(=O)CH3,
`
`(C5H5)2SO;
`
`alkoxy can include methoxy, ethoxy, n—propyloxy,
`isbpropyloxy and the different butoxy, pentoxy and
`hexyloxy isomers, cycloalkoxy can include cyclopentyloxy
`and cyclohexyloxy;
`
`cycloalkyl can include cyclopropyl, cyclobutyl,
`cyclopentyl, and cyclohexyl; and
`
`35
`
`cycloalkenyl can include cyclopentenyl and
`cyclohexenyl.
`
`

`

`W0 93/201 1 1
`
`PCI'/US93/03425
`
`10
`
`The term "halogen" or "halide“, either alone or in
`
`compound words such as "haloalkyl", denotes fluorine,
`chlorine, bromine or iodine.
`
`Alkoxyalkyl can include CH3OCH2, CH3OCH2CH2,
`CH3CH20CH2, CH3CH2CHQCH20CH2 and CH3CH20CH2CH2; and
`
`alkoxycarbonyl can include CH3OC(=O), CH3CH20C(=O),
`CH3CH2CH20C(=O),
`(CH3)2CHOC(=O) and the different
`
`butoxy—, pentoxy- or hexyloxycarbonyl isomers.
`
`A neutral electron donor is any ligand which, when
`
`removed from a metal center in its closed shell electron
`
`configuration, has a neutral charge, i.e., is a Lewis
`base.
`
`An anionic ligand is any ligand which when removed
`
`from a metal center in its closed shell electron
`
`configuration has a negative charge.
`
`The critical
`
`feature of the carbene compounds of this invention is
`
`the presence of the ruthenium or osmium in the +2
`
`oxidation state, an electron count of 16 and
`
`A wide variety of ligand moieties X,
`pentacoordination.
`Xi, L, and L1 can be present and the carbene compound
`will still exhibit its catalytic activity.
`
`A preferred embodiment of the compounds of the
`present invention is:
`
`-A compound of the invention of Formula I wherein:
`
`R and R1 are independently selected from
`
`hydrogen. vinyl. C1—C10 alkyl: aryl, Cl-Clo
`carboxylate, C2-C10 alkoxycarbonyl, C1-Clo
`
`alkoxy, aryloxy, each optionally substituted
`with C1—C5 alkyl, halogen, Cl—Cs alkoxy or
`
`with a phenyl group optionally substituted
`with halogen, C1-C5 alkyl or C1-C5 alkoxy;
`X and X1 are independently selected from
`
`halogen, hydrogen; or C1-Czo alkyl, aryl,
`
`C1-C20 alkoxide, aryloxide, C2-C20
`
`alkoxycarbonyl, arylcarboxylate, C1-C20
`
`10
`
`15
`
`20
`
`25
`
`30
`
`35
`
`

`

`W0 93/2011 1
`
`PCT/US93/03425
`
`11
`
`carboxylate, aryl or C1—C20 alkylsulfonate,
`
`C1-C20 alkylthio, C1-C20 alkylsulfonyl,
`
`C1-C20 alkylsulfinyl, each optionally
`
`substituted with C1—C5 alkyl, halogen, C1-C5
`
`alkoxy or with a phenyl group optionally
`
`substituted with halogen, Cl-C5 alkyl or
`
`C1—C5 alkoxy; and
`
`L and L1 are independently selected from
`
`phosphine, sulfonated phosphine, phosphite,
`
`phosphinite, phosphonite, arsine, stibine,
`
`ether, amine, amide, sulfoxide, carbonyl,
`
`nitrosyl, pyridine or thioether.
`
`A more preferred embodiment of Formula I comprises:
`
`A compound of the invention wherein:
`
`R and R1 are independently selected from
`
`hydrogen; vinyl, C1—C5 alkyl, phenyl,
`
`C2-C5 alkoxycarbonyl, C1-C5 carboxylate,
`
`C1-C5 alkoxy, phenoxy; each optionally
`
`substituted with C1-C5 alkyl, halogen,
`
`C1—C5 alkoxy or a phenyl group
`optionally substituted with halogen,
`C1-C5 alkyl or C1—C5 alkoxy;
`
`X and X1 are independently selected from Cl,
`
`Br, H, or benzoate, C1~C5 carboxylate,
`
`C1-C5 alkyl, phenoxy, C1—C5 alkoxy, C1-C5
`
`alkylthio, aryl, and C1—C5 alkyl
`
`sulfonate; each optionally substituted
`
`with C1—C5 alkyl or a phenyl group
`
`optionally substituted with halogen,
`
`C1—C5 alkyl or C1—C5 alkoxy;
`
`L and L1 are independently selected from
`
`aryl or C1-Clo alkylphosphine, aryl- or
`
`C1-C10 alkylsulfonated phosphine, aryl—
`
`or C1-C10 alkylphosphinite, aryl- or
`
`C1-C10 alkylphosphonite, aryl- or C1-C10
`
`m
`
`.0
`
`10
`
`15
`
`20
`
`25
`
`3O
`
`35
`
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`
`12
`
`alkylphosphite, aryl— or C1—Clo
`
`alkylarsine, aryl- or C1—C10 alkylamine,
`
`pyridine, aryl- or C1-Clo alkyl
`
`sulfoxide, aryl- or C1-C10 alkylether,
`
`or aryl- or C1-C10 alkylamide, each
`
`optionally substituted with a phenyl
`
`group optionally substituted with
`
`halogen, C1—C5 alkyl or C1-C5 alkoxy.
`
`A further preferred embodiment of Formula I
`
`10
`
`comprises:
`
`15
`
`20
`
`A compound of the present invention wherein:
`
`R and R1 are independently vinyl, H, Me, Ph;
`X and X1 are independently Cl, CF3C02, CH3C02
`
`CFHZCOZ,
`
`(CH3)3CO,
`
`(CF3)2(CH3)CO,
`
`(CF3)(CH3)2CO, PhO, MeO, EtO, tosylate,
`
`mesylate, or trifluoromethanesulfonate;
`and
`
`L and L1 are independently PMe3, PPh3,
`
`P(p-'I‘ol)3,' P(O"T01)31 PMeth, PPhMez,
`
`P(CF3)3, P(p-FC5H4)3, pyridine,
`
`P (p—CF3C5H4) 3,
`
`(p-F) Pyridine,
`
`(p—CF3)pyridine, P(C5H4-SO3Na)3 or
`
`P(CH2C5H4-SO3Na)3.
`
`25
`
`For any of the foregoing described preferred groups
`of compounds, any 2, 3, or 4 of x, X1, L, L1 can be
`
`taken together to form a chelating multidentate ligand.
`Examples of bidentate ligands include, but are not
`
`limited to, bisphosphines, dialkoxides,
`
`alkyldiketonates, and aryldiketonates. Specific
`
`examples include thPCHzCHzPth,
`
`thASCHzCHzASth,
`
`thPCH2CHzc(CF3)O—, binaphtholate dianions, pinacolate
`
`dianions, Me2P(CH2)2PMe2 and ’0C(CH3)2(CH3)2CO‘.
`
`Preferred.bidentate ligands are thPCHzCHZPth and
`
`MegPCHZCHzPMez. Tridentate ligands include, but are not
`
`limited to,
`
`(CH3)2NCH2CH2P(Ph)CH2CH2N(CH3)2. Other
`
`30
`
`35
`
`

`

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`PCT/US93/03425
`
`13
`
`preferred tridentate ligands are those in which X, L,
`and L1 are taken together to be cyclopentadienyl,
`indenyl or fluorenyl, each optionally substituted with
`C2-C20 alkenyl, C2—C20 alkynyl, C1—C20 alkyl, aryl, C1-C20
`carboxylate, C1-C20 alkoxy, C2-C20 alkenyloxy, C2-C20
`alkynyloxy, aryloxy, C2—C20 alkoxycarbonyl, C1-C20
`alkylthio, C1—C20 alkylsulfonyl, C1-C20 alkylsulfinyl,
`each optionally substituted with C1—C5 alkyl, halogen,
`C1—C5 alkoxy or with a phenyl group optionally
`substituted with halogen, C1—C5 alkyl or C1—C5 alkoxy.
`
`More preferably in compounds of this type, X, L, and L1
`
`are taken together to be cyclopentadienyl or indenyl,
`each optionally substituted with hydrogen; vinyl, C1-Clo
`alkyl, aryl, C1—Clo carboxylate, C2—C10 alkoxycarbonyl,
`C1-Clo alkoxy, aryloxy, each optionally substituted with
`C1-C5 alkyl, halogen, C1-C5 alkoxy or with a phenyl group
`optionally substituted with halogen, C1-C5 alkyl or C1—C5
`alkoxy. Most preferably, X, L, and L1 are taken
`
`10
`
`15
`
`20
`
`together to be cyclopentadienyl, optionally substituted
`with vinyl, hydrogen, Me or Ph. Tetradentate ligands
`include, but are not limited to
`
`02C (CH2) 2P (Ph) (CH2) 2P (Ph) (CH2) 2C02, phthalocyanines, and
`porphyrins.
`
`25
`
`The most preferred carbene compounds of the present
`invention include:
`
` CHILL:
`Ph
`(3/
`PPh3 H>_< Ph
`
`PPh3
`
` C12+s
`PPh3
`
`' H
`
`C/
`>=<
`
`Ph
`
`an
`
`A)
`
`u
`
`

`

`W0 93/201 l 1
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`PCI'1US93/03425
`
`14
`
`C
`
`3
`
`c
`
`PPh3
`o
`
`,I \ I
`Ru
`\
`\0/ ll’Ph
`3 H
`
`C
`
`H
`
`/
`>—<
`
`+
`
`-
`
`3
`
`Cl
`
`Ph
`
`Ph
`
`/
`
`0 H
`
`F3CCO
`
`PPh
`
`3
`
`H
`
`m
`
`\Rgrcx
`Fgcco PPh3 >_<
`('5
`H
`Ph
`
`, and
`
`Ph
`
`Ph
`
`(C5M65)C1Ru=C
`
`H
`/
`
`>=<
`
`H
`
`The compounds of thepresent invention can be
`
`prepared in several different ways, each of which is
`described below.
`
`5
`
`The most general method for preparing the compounds
`of this invention comprises reacting (XX1MLnL1m)p with a
`cyclopropene or phosphorane in the presence of a solvent
`
`to produce a carbene complex, as shown in the equations.-
`
`

`

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`
`15
`
`L
`
`1
`1
`(XX MLnL m)p +
`
`R4
`5 \\ ___ R
`R ——P
`6/’
`R
`
`R
`
`1
`
`X
`R
`I’
`\\\£4
`__> =\ 1
`z//
`R
`xl
`
`Ll
`
`+ PR4R5R°
`
`wherein:
`
`IJL.
`
`M, X, X1, L, L1, n, m, p, R2, R3, R4, R5, and R5 are
`
`as defined above. Preferably, R2, R3, R4, R5,
`and R6 are independently selected from the group
`consisting of C1—C6 alkyl or phenyl.
`
`Examples of solvents for this reaction include
`
`organic, protic, or aqueous solvents which are inert
`
`under the reaction conditions, such as:
`
`aromatic
`
`hydrocarbons, chlorinated hydrocarbons, ethers,
`aliphatic hydrocarbons, alcohols, water, or mixtures
`thereof. Preferred solvents include benzene,
`toluene,
`p-xylene, methylene chloride, dichloroethane,
`dichlorobenzene,
`tetrahydrofuran, diethylether, pentane,
`methanol, ethanol, water, or mixtures thereof. More
`
`toluene, p-xylene,
`the solvent is benzene,
`preferably,
`methylene chloride, dichloroethane, dichlorobenzene,
`tetrahydrofuran, diethylether, pentane, methanol,
`ethanol, or mixtures thereof.
`
`A suitable temperature range is from about -20°C to
`
`about 125°C, preferably 35°C to 90°C, and more
`
`preferably 50°C to 65°C. Pressure is not critical but
`
`may depend on the boiling point of the solvent used,
`i.e., use sufficient_pressure to maintain a solvent
`liquid phase. Reaction times are not critical, and can
`be from several minutes to 48 hours.
`The reactions are
`
`10
`
`15
`
`20
`
`25
`
`‘M
`
`1V
`
`1\
`
`

`

`W0 93/201 1 l
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`
`16
`
`generally carried out
`
`in an inert atmosphere, most
`
`preferably nitrogen or argon.
`
`The reaction is usually carried out by dissolving
`the compound (XXlMLnle)p,
`in a suitable solvent, adding
`
`the cyclopropene (preferably in a solvent) to a stirred
`
`solution of the compound, and optionally heating the
`
`mixture until the reaction is complete.
`
`The progress of
`
`the reaction can be monitored by any of several standard
`
`analytical techniques, such as infrared or nuclear
`
`magnetic resonance.
`
`Isolation of the product can be
`
`accomplished by standard procedures, such as evaporating
`
`the solvent, washing the solids (e.g., with alcohol or
`
`benzene), and then recrystallizing the desired carbene
`
`complex. Whether the moieties X, X1, L, or L1 are
`
`(unidentate)
`
`ligands or some taken together to form
`
`multidentate ligands will depend on the starting
`
`compound which simply carries these ligands over into
`
`the desired carbene complex.
`
`10
`
`15
`
`20
`
`In one variation of this general procedure,
`reaction is conducted in the presence of HgClz,
`
`the
`
`preferably 0.01 to 0.2 molar equivalents, more
`
`preferably 0.05 to 0.1 equivalents, based on xleLnle.
`
`In this variation,
`
`the reaction temperature is
`
`preferably 15°C to 65°C.
`
`In a second variation of the general procedure,
`
`the
`
`reaction is conducted in the presence of ultraviolet
`
`In this variation,
`radiation.
`is preferably ~20°C to 30°C.
`
`the reaction temperature
`
`It is also possible to prepare carbene complexes of
`
`For example, L
`this invention by ligand exchange.
`and/or L1 can be replaced by a neutral electron donor,r
`L2,
`in compounds of Formula I by reacting L2 with
`
`compounds of Formula I wherein L, L1, and L2 are
`
`independently selected from phosphine, sulfonated
`
`phosphine, phosphite, phosphinite, phosphonite, arsine,
`
`25
`
`3O
`
`35
`
`

`

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`
`17
`
`stibine, ether, amine, amide, sulfoxide, carbonyl,
`nitrosyl, pyridine or thioether. Similarly, X and/or X1
`can be replaced by an anionic ligand, Y,
`in compounds of
`Formula I by reacting MlY with compounds of Formula I,
`wherein X and X1 are independently selected from
`halogen, hydrogen, or C1-C2() alkyl, aryl, C1-C20
`alkoxide, aryloxide, C2-C20 alkoxycarbonyl,
`'arylcarboxylate, C1-C20 carboxylate, aryl or C1-C20
`alkylsulfonate, C1-C20 alkylthio, C1-C20 alkylsulfonyl,
`C1-C20 alkylsulfinyl, each optionally substituted with
`C1—C5 alkyl, halogen, C1-C5 alkoxy or with a phenyl group
`optimally substituted with halogen, C1-C5 alkyl or C1-C5
`alkoxy. These ligand exchange reactions are typically
`carried out
`in a solvent which is inert under the
`
`reaction conditions. Examples of solvents include those
`
`described above for the preparation of the carbene
`complex.r
`
`The compounds of this invention are useful as
`
`catalysts in the preparation of a wide variety of
`polymers which can be formed by ring—opening metathesis
`polymerization of cyclic olefins. Therefore, one
`embodiment of this invention is an improved
`
`polymerization process comprising metathesis
`
`polymerization of a cyclic olefin, wherein the-
`
`~improvement comprises conducting the polymerization in
`the presence of a catalytic amount of a compound of
`Formula I.
`The polymerization reaction is exemplified
`for norbornene in the following equation:
`
`compound
`of Formula I
`
`as catalyst
`
`11
`
`I
`
`10
`
`15
`
`20
`
`25
`
`30
`
`wherein n is the repeat unit of the polymeric chain.
`
`

`

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`
`18
`
`Examples of cyclic olefins for this polymerization
`
`process include norbornene, norbornadiene, cyclopentene,
`
`dicyclopentadiene, cycloheptene, cyclo—octene,
`
`7-oxanorbornene, 7-oxanorbornadiene, and cyclododecene.
`
`The polymerization reaction is generally carried
`
`out in an inert atmosphere by dissolving a catalyticr
`
`amount of a compound of Formula I in a solvent and
`
`adding the cyclic olefin, optionally dissolved in a
`
`solvent,
`
`to the catalyst solution. Preferably,
`
`the
`
`reaction is agitated (e.g., stirred).
`
`The progress of
`
`the reaction can be monitored by standard techniques,
`
`e.g., nuclear magnetic resonance spectroscopy.
`
`Examples of solvents for the polymerization
`
`reaction include organic, protic, or aqueous solvents
`
`which are inert under the polymerization conditions,
`
`such as:
`
`aromatic hydrocarbons, chlorinated
`
`hydrocarbons, ethers, aliphatic hydrocarbons, alcohols,
`
`water, or mixtures thereof. Preferred solvents include
`
`benzene,
`
`toluene, p—xylene, methylene chloride,
`
`dichloroethane, dichlorobenzene,
`
`tetrahydrofuran,
`
`diethylether, pentane, methanol, ethanol, water, or
`
`mixtures thereof. More preferably,
`
`the solvent is
`
`benzene,
`
`toluene, p-xylene, methylene chloride,
`
`dichloroethane, dichlorobenzene,
`
`tetrahydrofuran,
`
`diethylether, pentane, methanol, ethanol, or mixtures
`
`thereof. Mbst preferably,
`
`the solvent is toluene or a
`
`mixture of benzene and methylene chloride.
`
`The
`
`solubility of the polymer formed in the polymerization
`reaction will depend on the choice of solvent and the
`
`molecular weight of the polymer obtained.
`
`Reaction temperatures can range from 0°C to 100°C,
`rand are preferably 25°C to 45°C.
`The ratio of catalyst
`to olefin is not critical, and can range from 1:5 to
`
`1:10,000, preferably 1:10 to 1:1,000.
`
`10
`
`15
`
`20
`
`25
`
`30
`
`

`

`W0 93/201 I 1
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`PCI‘/ US93/03425
`
`19
`
`Because the compounds of Formula I are stable in
`
`the presence of protic solvents,
`
`the polymerization
`
`reaction may also be conducted in the presence ofra
`
`protic solvent. This is very unusual among metathesis
`
`catalysts and provides a distinct advantage for the
`
`process of this invention over the processes of the
`
`prior art. Other advantages of the polymerization
`
`10
`
`process of this invention derive from the fact that the
`
`compounds of Formula I are well—defined, stable Ru or Os
`
`carbene complexes providing high catalytic activity.
`Using such compounds as catalysts allows control of the
`
`rate of initiation, extent of initiation, and the amount
`
`of catalyst. Also,
`
`the well-defined ligand environment
`
`15
`
`of these complexes provides flexibility in modifying and
`fine—tuning their activity level, solubility, and
`
`stability.
`
`In addition,
`
`these modifications enable ease
`
`of recovery of catalyst.
`
`20
`
`25
`
`30
`
`35
`
`n
`
`'
`
`' n
`
`f
`
`' P
`
`r
`
`i n
`
`f
`
`m
`
`of this Invention from nglgprgpenes:
`
`A 50 ml Schlenk flask equipped with a magnetic
`stirbar is charged with (MXXanle)p (0.1 mmol)
`inside a
`nitrogen-filled drybox. Methylene chloride (2 ml)
`is
`
`added to dissolve the complex followed by 25 ml of
`
`benzene to dilute the solution. One equivalent of a
`
`cyclopropene is then added to this solution.
`
`The
`
`reaction flask is then capped with a stopper,
`
`removed
`
`from the box, attached to a reflux condenser under argon
`and heated at 55°C.
`The reaction is then monitored by
`NMR spectroscopy until all the reactants have been
`
`rconverted to product. At the end of the reaction,
`the
`solution is allowed to cool to room temperature under
`
`argon and then filtered into another Schlenk flask via a
`
`cannula filter. All solvent is then removed in vacuo to
`
`give a solid. This solid is then washed with a solvent
`
`

`

`W0 93/201 1 1
`
`PCT/US93/03425
`
`20
`
`in which the by—product will be soluble but the desired
`
`product will not. After the washing supernatant is
`
`removed,
`
`the resulting solid powder is dried in vacuo
`
`overnight. Further purification via crystallization can
`
`be performed if necessary.
`
`The abbreviations Me, Ph, and THE used herein refer
`
`to methyl, phenyl, and tetrahydrofuran, respectively.
`
`Representative compounds of the present invention
`
`which are prepared in accordance with the procedure
`
`described above are exemplified in Table I.
`
`10
`
`15
`
`20
`
`25
`
`30
`
`

`

`W0 93/2011]
`
`PCT/US93/03425
`
`21
`
`Ncmouzo
`
`mzmcmm
`
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`
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`
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`
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`
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`
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`
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`
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`
`do
`
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`
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`
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`
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`
`5m
`
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`
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`
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`
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`
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`
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`
`5%
`
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`
`
`
`AHHVESflcwnunuAwaflnmmonm
`
`

`

`W0 93/2011]
`
`PCl"/US93/03425
`
`22
`
`oz
`
`i
`
`22
`
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`
`ow;
`
`egg
`
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`
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`
`.HHvsnacwnuzu
`
`

`

`W0 93/2011]
`
`PCI‘/US93/03425
`
`.E
`
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`
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`
`

`

`W0 93/201 1 1
`
`PCI‘/US93/03425
`
`24
`
`EXAMPLE I
`
`Synthesis of
`
`C12(PPh3)2Ru =/—<Ph
`
`1
`
`Ph
`
`10
`
`15
`
`20
`
`25
`
`3O
`
`In a typical reaction, a 200 ml Schlenk flask
`equipped with a magnetic stirbar was charged with
`RuClz(PPh3)4 (6.00 g, 4.91 mmol)
`inside a nitrogen-filled
`
`drybox. Methylene chloride (40 mL) was added to
`
`dissolve the complex followed by 100 mL of benzene to
`
`dilute the solution-
`
`3,3-Diphenylcyclopropene (954 mg,
`
`1.01 equiv) was then added to the solution via pipette.
`
`The reaction flask was capped with a stopper,
`
`removed
`
`from the box, attached to a reflux condenser under argon
`
`and heated at 53°C for 11 h. After allowing the
`
`solution to cool to room temperature, all the solvent
`
`was removed in vacuo to give a dark yellow—brown solid.
`
`Benzene (10 mL) was added to the solid and subsequent
`
`swirling of the mixture broke the solid into a fine
`
`powder. Pentane (80 mL) was then slowly added tO'the
`
`The
`mixture via cannula while stirring vigorously.
`mixture was stirred at room temperature for 1 h and
`allowed to settle before the supernatant was removed via
`
`cannula filtration. This washing procedure was repeated
`
`two more times to ensure the complete removal of all
`
`phosphine by—products.
`
`The resulting solid was then
`
`dried under vacuum overnight to afford 4.28 g (98%) of
`
`Compound 1 as a yellow powder with

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