Mixed-metal cluster chemistry VI 1

Abstract

Reactions of CpMoIr3(μ-CO)3(CO)8 (1) with stoichiometric amounts of phosphines afford the substitution products CpMoIr3(μ-CO)3(CO)8-x(L)x (L = PPh3, x = 1 (2), 2 (3); L = PMe3, x = 1 (4), 2 (5), 3 (6)) in fair to good yields (23-54%); the yields of both 3 and 6 are increased on reacting 1 with excess phosphine. Products 2-5 are fluxional in solution, with the interconverting isomers resolvable at low temperatures. A structural study of one isomer of 2 reveals that the three edges of an MoIr2 face of the tetrahedral core are spanned by bridging carbonyls, and that the indium-bound triphenylphosphine ligates radially and the molybdenum-bound cyclopentadienyl coordinates axially with respect to this MoIr2 face. Information from this crystal structure, 31P NMR data (both solution and solid-state), and results with analogous tungsten-triiridium and tetrairidium clusters have been employed to suggest coordination geometries for the isomeric derivatives. Show more