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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ASJC Scopus subject areas

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

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