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

Abstract

Reaction of equimolar quantities of Me 3SnCCRCCSnMe 3 [R = p-C 6H 4; p-C 6H 2(CH 3)2; p-C 6H 4- p-C 6H 4] with the group 10 metal dihalide complexes, [M(X nBU 3) 2Cl 2] (M = Pt, Pd, Ni; X = P, As; Bu = butyl) affords the polymeric species trans-[−M(X nBU 3) 2(-CCRCC-)] n in excellent yields. By varying the stoichiometry of these reactions, complexes of the type trans-[M(X nBU 3) 2(−CCRCCSnMe 3) 2] and trans-[ClM(X nBU 3) 2CCRCCM(X n BU 3) 2Cl], which are precursors to higher oligomers, can be prepared. Treatment of the former with an excess of trans-[M(X nBU 3) 2Cl 2] affords the trimetallic compound trans-[ClM(X nBU 3) 2(−CCRCC−)M(X nBU 3) 2(−CCRCC−)M(X nBU 3) 2Cl], while reaction of the latter with two equivalents of Me 3SnCCRCCSnMe3 followed by two equivalents of trans-[M(X nBu 3) 2Cl 2] gives the complex trans-[ClM(X nBU 3) 2(−CCRCC−)M(X nBu 3) 2(−CCRCC−)M(X nBu 3) 2(−CCRCC−)M(X nBu 3) 2Cl]. Treatment of the complex [Rh(PPhl) 3Cl] (Ph = Phenyl) with one equivalent of Me 3SnCCRCCSnMe 3 [R = p-C 6H 4- p-C 6H 4] gives the polymeric species [−Rh(PPh 3) 2(SnMe 3)(−CCRCC−)] n . Model compounds for other rhodium-containing σ-acetylide complexes have been obtained from the reaction between the complex [Rh(PMe 3) 4Cl] (Me = CH 3) and Me 3SnCCC 6H 5 which yields the compound mer,trans-[Rh(PMe 3) 3-(SnMe 3)(−CCC 6H 5) 2] via the intermediate [Rh(PMe 3) 4(−CH 5]. Reaction of [Rh(PMe 3) 4Cl] with one equivalent of Me 3SnCCRCCSnMe3 [R = p-C 6H 4- p-C 6H 4] yields the polymer mer,trans[−Rh(PMe 3) 3(SnMe 3)(−CCRCC−)] n .