Oxidation of η6-arene Complexes of Group VI Metals. Part 2. A Convenient Preparation of Mo2I4(CO)8, its Reactivity and its Crystal and Molecular Structure

Fausto Calderazzo (1) , Rinaldo Poli (1) , Pier Francesco Zanazzi (2)

1 University of Pisa - Università di Pisa
2 UNIPG - Università degli Studi di Perugia = University of Perugia

The ionic [MoI(CO)3(η6-arene)][Mo2I5(CO)6] compounds (arene = C6H5Me, 2; 1,4-C6H4Me2, 3; 1,3,5-C6H3Me3, 4) react with CO at atmospheric pressure and room temperature in toluene to give Mo2I4(CO)8, 1, in yields as high as 88%. Compound l has been studied by X-ray diffraction methods. Crystal data: triclinic, space group P-1, a = 10.242(3), b = 7.331(3), c = 6.937(3) Å. α = 112.88(2), β = 102.93(2), γ = 81.00(2)°, Z = 1, R = 0.041 for 495 observed reflections. Disproportionation of 1 into MoI3 and Mo2I2(CO)8 has been observed by interaction with water or by thermal treatment in toluene. Compound 1 reacts with Lewis bases to afford MoI2(CO)3L2 and with [NBu4]I to yield the [MoI3(CO)4]- anion. Reduction of l to Mo2I2(CO)8 can be accomplished with a number of reducing agents.

Domaines: Chimie de coordination

Fausto Calderazzo, Rinaldo Poli, Pier Francesco Zanazzi. Oxidation of η6-arene Complexes of Group VI Metals. Part 2. A Convenient Preparation of Mo2I4(CO)8, its Reactivity and its Crystal and Molecular Structure. Gazzetta Chimica Italiana, 1988, 118, pp.583-587. ⟨hal-03574293⟩