Pentamethylcyclopentadienyl-rhodium and -iridium complexes. Part 18. The reactions of [M(C5Me5)(sol)3][PF6]2(M = Rh or Ir; sol = MeCn, Me2CO, or MeOH) with Mono-, Di-, and Tri-olefins

Abstract

Reaction of [M(C₅Me₅)(MeCN)₃][PF₆]₂(1; M = Rh or Ir) with bicyclo[2.2.1]heptadiene (nbd) gave [M(C₅Me₅)(nbd)(MeCN)][PF₆]₂. Cycle-octa-1,5-diene (cod) underwent deprotonation when treated with (1) or [M(C₅Me₅)(Me₂CO)₃][PF₆]₂, (3), to give the 1–3:5,6-η-cyclo-octadienyl complexes [M(C₅Me₅)(C₈H₁₁)][PF₆](M = Rh or Ir); the iridium complex underwent hydride attack by [BH₄]^– to give [Ir(C₅Me₅)(cod)]. Cyclopentadiene, dicyclopentadiene, and propene were all complexed with deprotonation on reaction with (3) to give [M(C₅Me₅)(C₅H₅)][PF₆], the 1–3:5,6-η-(4,7-methano)-3a,4,7,7a-tetrahydroindenyl complexes, [M(C₅Me₅)(C₁₀H₁₁)][PF₆](M = Rh or Ir) and [Ir(C₅Me₅)(η³-C₃H₅)(η²-C₅H₅)][PF₆] respectively. In contrast, cycloheptatriene underwent nucleophilic attack by the solvent when treated with [M(C₅Me₅)(YH)_x][PF₆]₂[3; YH = Me₂CO, M = Rh or Ir; YH = MeOH, M = Rh] to give the 6-exo-acetonyl- or 6-exo-methoxy-1–5-η-cycloheptadienyl complex [M(C₅Me₅){C₇H₈(Y)}][PF₆]. The ¹H and ¹³C spectra of the products are discussed.