Synthesis and reactivity of the novel hydride derivative RhHCl(TIMP3) (HTIMP3 = tris[1-(diphenylphosphino)-3-methyl-1H-indol-2-yl]methane)

Abstract

The reaction of HTIMP₃ (HTIMP₃ = tris[1-(diphenylphosphino)-3-methyl-1H-indol-2-yl]methane) with [RhCl(COD)]₂ and Rh(acac)(CO)₂ produces RhHCl(TIMP₃) (1H) and Rh(TIMP₃)(CO) (2), respectively, both exhibiting tetradentate κC,κ³P-coordination of the TIMP₃ moiety. The reaction of RhHCl(TIMP₃) with nucleophiles (L) in the presence of AgBF₄ or AgPF₆ produces different compounds depending on the nature of L. Indeed, cationic Lewis adducts of formula [RhH(L)(TIMP₃)]⁺ (2H⁺-5H⁺) are obtained when L is CO, CNCH₂Ph, pyridine or CH₂CHCN. On the other hand, when the incoming nucleophile is CH₃COOH the hydride-free complex [Rh(CH₃COO)(TIMP₃)]⁺ (6⁺) is obtained. Finally, the reaction of RhHCl(TIMP₃) with PhCCPh and CH₂CHCOOMe in the presence of AgPF₆ leads to the insertion products [Rh(PhCCHPh)(TIMP₃)]⁺ (7⁺) and [Rh(CH₂CH₂COOMe)(TIMP₃)]⁺ (8⁺), respectively. The solid state structure has been determined by single crystal X-ray diffraction in selected cases (1H, 6⁺).