Isocyanide complexes of rhodium and iridium. Part I. Tetrakisisocyanide species, their oxidative addition reactions, and some allyl complexes

Abstract

The rhodium(I) and iridium(I) isocyanide complexes [M(CNR)₄]Z (M = Rh, Z = PF₆, R = Me, Prⁱ. cyclohexyl, Bu^t, p-MeOC₆H₄, p-MeC₆H₄, or p-ClC₆H₄; M = Rh, Z = Cl, R = Bu^t or p-ClC₆H₄; M = Ir, Z = PF₆, R = Bu_t or p-ClC₆H₄) have been prepared. These undergo oxidative addition reactions giving trans-[M(CNR)₄XY]⁺(various R; X = Cl, Y = Cl, PhCH₂, C₃H₅, C₃H₄Me, MeCO, HgCl, or SnCl₃; X = Br, Y = Br, CN, PhCH₂, or C₃H₅; X = I, Y = I, Me, CF₃, or C₃F₇). Addition of NO⁺, p-MeC₆H₄N₂⁺, or SO₂ afforded [Rh(NO)(CNR)₄][PF₆]₂(R = Prⁱ, cyclohexyl, or Bu^t), [Rh{N₂(p-MeC₆H₄)}(CNBu^t)₄][PF₆]₂ and [Rh(SO₂)(CNR)₄][PF₆](R = Prⁱ or p-MeC₆H₄), respectively. Treatment of [Rh(π-C₃H₆)₂Cl]₂ with one or two moles of RNC (R =p-MeC₆H₄), afforded either [Rh(π-C₃H₅)₂(CNR)Cl] or [Rh(π-C₃H₅)(σ-C₃H₅)(CNR)₂Cl].