Synthesis of monomeric, oligomeric and polymeric σ-acetylide complexes of platinum, palladium, nickel and rhodium

Muhammad S. Khan, Simon J. Davies, Ashok K. Kakkar, David Schwartz, Bing Lin, Brian F G Johnson, Jack Lewis

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Abstract

Reaction of equimolar quantities of Me3SnCCRCCSnMe3 [R = p-C6H4; p-C6H2(CH3)2; p-C6H4-p-C6H4] with the group 10 metal dihalide complexes, [M(XnBU3)2Cl2] (M = Pt, Pd, Ni; X = P, As; Bu = butyl) affords the polymeric species trans-[-M(XnBU3)2(-CCRCC-)]n in excellent yields. By varying the stoichiometry of these reactions, complexes of the type trans-[M(XnBU3)2(-CCRCCSnMe3)2] and trans-[ClM(XnBU3)2CCRCCM(Xn BU3)2Cl], which are precursors to higher oligomers, can be prepared. Treatment of the former with an excess of trans-[M(XnBU3)2Cl2] affords the trimetallic compound trans-[ClM(XnBU3)2(-CCRCC-)M(XnBU3)2(-CCRCC-)M(XnBU3)2Cl], while reaction of the latter with two equivalents of Me3SnCCRCCSnMe3 followed by two equivalents of trans-[M(XnBu3)2Cl2] gives the complex trans-[ClM(XnBU3)2(-CCRCC-)M(XnBu3)2(-CCRCC-)M(XnBu3)2(-CCRCC-)M(XnBu3)2Cl]. Treatment of the complex [Rh(PPhl)3Cl] (Ph = Phenyl) with one equivalent of Me3SnCCRCCSnMe3 [R = p-C6H4-p-C6H4] gives the polymeric species [-Rh(PPh3)2(SnMe3)(-CCRCC-)]n. Model compounds for other rhodium-containing σ-acetylide complexes have been obtained from the reaction between the complex [Rh(PMe3)4Cl] (Me = CH3) and Me3SnCCC6H5 which yields the compound mer,trans-[Rh(PMe3)3-(SnMe3)(-CCC6H5)2] via the intermediate [Rh(PMe3)4(-CH5]. Reaction of [Rh(PMe3)4Cl] with one equivalent of Me3SnCCRCCSnMe3 [R = p-C6H4-p-C6H4] yields the polymer mer,trans[-Rh(PMe3)3(SnMe3)(-CCRCC-)]n.

Original languageEnglish
Pages (from-to)87-97
Number of pages11
JournalJournal of Organometallic Chemistry
Volume424
Issue number1
DOIs
Publication statusPublished - Feb 4 1992

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Rhodium
Coordination Complexes
Palladium
Metal complexes
Platinum
Nickel
rhodium
Oligomers
Stoichiometry
palladium
Polymers
platinum
nickel
synthesis
oligomers
stoichiometry
polymers
metals

ASJC Scopus subject areas

  • Biochemistry
  • Chemical Engineering (miscellaneous)
  • Inorganic Chemistry
  • Organic Chemistry
  • Physical and Theoretical Chemistry
  • Materials Science (miscellaneous)
  • Materials Chemistry

Cite this

Synthesis of monomeric, oligomeric and polymeric σ-acetylide complexes of platinum, palladium, nickel and rhodium. / Khan, Muhammad S.; Davies, Simon J.; Kakkar, Ashok K.; Schwartz, David; Lin, Bing; Johnson, Brian F G; Lewis, Jack.

In: Journal of Organometallic Chemistry, Vol. 424, No. 1, 04.02.1992, p. 87-97.

Research output: Contribution to journalArticle

Khan, Muhammad S. ; Davies, Simon J. ; Kakkar, Ashok K. ; Schwartz, David ; Lin, Bing ; Johnson, Brian F G ; Lewis, Jack. / Synthesis of monomeric, oligomeric and polymeric σ-acetylide complexes of platinum, palladium, nickel and rhodium. In: Journal of Organometallic Chemistry. 1992 ; Vol. 424, No. 1. pp. 87-97.
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abstract = "Reaction of equimolar quantities of Me3SnCCRCCSnMe3 [R = p-C6H4; p-C6H2(CH3)2; p-C6H4-p-C6H4] with the group 10 metal dihalide complexes, [M(XnBU3)2Cl2] (M = Pt, Pd, Ni; X = P, As; Bu = butyl) affords the polymeric species trans-[-M(XnBU3)2(-CCRCC-)]n in excellent yields. By varying the stoichiometry of these reactions, complexes of the type trans-[M(XnBU3)2(-CCRCCSnMe3)2] and trans-[ClM(XnBU3)2CCRCCM(Xn BU3)2Cl], which are precursors to higher oligomers, can be prepared. Treatment of the former with an excess of trans-[M(XnBU3)2Cl2] affords the trimetallic compound trans-[ClM(XnBU3)2(-CCRCC-)M(XnBU3)2(-CCRCC-)M(XnBU3)2Cl], while reaction of the latter with two equivalents of Me3SnCCRCCSnMe3 followed by two equivalents of trans-[M(XnBu3)2Cl2] gives the complex trans-[ClM(XnBU3)2(-CCRCC-)M(XnBu3)2(-CCRCC-)M(XnBu3)2(-CCRCC-)M(XnBu3)2Cl]. Treatment of the complex [Rh(PPhl)3Cl] (Ph = Phenyl) with one equivalent of Me3SnCCRCCSnMe3 [R = p-C6H4-p-C6H4] gives the polymeric species [-Rh(PPh3)2(SnMe3)(-CCRCC-)]n. Model compounds for other rhodium-containing σ-acetylide complexes have been obtained from the reaction between the complex [Rh(PMe3)4Cl] (Me = CH3) and Me3SnCCC6H5 which yields the compound mer,trans-[Rh(PMe3)3-(SnMe3)(-CCC6H5)2] via the intermediate [Rh(PMe3)4(-CH5]. Reaction of [Rh(PMe3)4Cl] with one equivalent of Me3SnCCRCCSnMe3 [R = p-C6H4-p-C6H4] yields the polymer mer,trans[-Rh(PMe3)3(SnMe3)(-CCRCC-)]n.",
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T1 - Synthesis of monomeric, oligomeric and polymeric σ-acetylide complexes of platinum, palladium, nickel and rhodium

AU - Khan, Muhammad S.

AU - Davies, Simon J.

AU - Kakkar, Ashok K.

AU - Schwartz, David

AU - Lin, Bing

AU - Johnson, Brian F G

AU - Lewis, Jack

PY - 1992/2/4

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N2 - Reaction of equimolar quantities of Me3SnCCRCCSnMe3 [R = p-C6H4; p-C6H2(CH3)2; p-C6H4-p-C6H4] with the group 10 metal dihalide complexes, [M(XnBU3)2Cl2] (M = Pt, Pd, Ni; X = P, As; Bu = butyl) affords the polymeric species trans-[-M(XnBU3)2(-CCRCC-)]n in excellent yields. By varying the stoichiometry of these reactions, complexes of the type trans-[M(XnBU3)2(-CCRCCSnMe3)2] and trans-[ClM(XnBU3)2CCRCCM(Xn BU3)2Cl], which are precursors to higher oligomers, can be prepared. Treatment of the former with an excess of trans-[M(XnBU3)2Cl2] affords the trimetallic compound trans-[ClM(XnBU3)2(-CCRCC-)M(XnBU3)2(-CCRCC-)M(XnBU3)2Cl], while reaction of the latter with two equivalents of Me3SnCCRCCSnMe3 followed by two equivalents of trans-[M(XnBu3)2Cl2] gives the complex trans-[ClM(XnBU3)2(-CCRCC-)M(XnBu3)2(-CCRCC-)M(XnBu3)2(-CCRCC-)M(XnBu3)2Cl]. Treatment of the complex [Rh(PPhl)3Cl] (Ph = Phenyl) with one equivalent of Me3SnCCRCCSnMe3 [R = p-C6H4-p-C6H4] gives the polymeric species [-Rh(PPh3)2(SnMe3)(-CCRCC-)]n. Model compounds for other rhodium-containing σ-acetylide complexes have been obtained from the reaction between the complex [Rh(PMe3)4Cl] (Me = CH3) and Me3SnCCC6H5 which yields the compound mer,trans-[Rh(PMe3)3-(SnMe3)(-CCC6H5)2] via the intermediate [Rh(PMe3)4(-CH5]. Reaction of [Rh(PMe3)4Cl] with one equivalent of Me3SnCCRCCSnMe3 [R = p-C6H4-p-C6H4] yields the polymer mer,trans[-Rh(PMe3)3(SnMe3)(-CCRCC-)]n.

AB - Reaction of equimolar quantities of Me3SnCCRCCSnMe3 [R = p-C6H4; p-C6H2(CH3)2; p-C6H4-p-C6H4] with the group 10 metal dihalide complexes, [M(XnBU3)2Cl2] (M = Pt, Pd, Ni; X = P, As; Bu = butyl) affords the polymeric species trans-[-M(XnBU3)2(-CCRCC-)]n in excellent yields. By varying the stoichiometry of these reactions, complexes of the type trans-[M(XnBU3)2(-CCRCCSnMe3)2] and trans-[ClM(XnBU3)2CCRCCM(Xn BU3)2Cl], which are precursors to higher oligomers, can be prepared. Treatment of the former with an excess of trans-[M(XnBU3)2Cl2] affords the trimetallic compound trans-[ClM(XnBU3)2(-CCRCC-)M(XnBU3)2(-CCRCC-)M(XnBU3)2Cl], while reaction of the latter with two equivalents of Me3SnCCRCCSnMe3 followed by two equivalents of trans-[M(XnBu3)2Cl2] gives the complex trans-[ClM(XnBU3)2(-CCRCC-)M(XnBu3)2(-CCRCC-)M(XnBu3)2(-CCRCC-)M(XnBu3)2Cl]. Treatment of the complex [Rh(PPhl)3Cl] (Ph = Phenyl) with one equivalent of Me3SnCCRCCSnMe3 [R = p-C6H4-p-C6H4] gives the polymeric species [-Rh(PPh3)2(SnMe3)(-CCRCC-)]n. Model compounds for other rhodium-containing σ-acetylide complexes have been obtained from the reaction between the complex [Rh(PMe3)4Cl] (Me = CH3) and Me3SnCCC6H5 which yields the compound mer,trans-[Rh(PMe3)3-(SnMe3)(-CCC6H5)2] via the intermediate [Rh(PMe3)4(-CH5]. Reaction of [Rh(PMe3)4Cl] with one equivalent of Me3SnCCRCCSnMe3 [R = p-C6H4-p-C6H4] yields the polymer mer,trans[-Rh(PMe3)3(SnMe3)(-CCRCC-)]n.

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