Oxidation of η6-arene Complexes of Group VI Metals. Part 4. Molybdenum(II)-arene-carbonyl Compounds Containing Polyiodides

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 reaction of Mo2I4(CO)8 with [MoI(CO)3(η6-C6Me6)]I3 affords [MoI(CO)3(η6-C6Me6)][MoI2(I3)(CO)4], 1, containing a coordinated tri-iodide ligand, as the major product. The reaction also affords small amounts of the complex [MoI(CO)3(η6-C6Me6)]I5, 2. Compound 2 has also been synthesized by reacting [MoI(CO)3(η6-C6Me6)]I3 with I2 in equimolar amounts or by interaction of Mo(CO)3(η6-C6Me6) with I2 in 1:3 molar ratio. The penta-iodide anions in compound 2 are arranged in an infinite chain of alternating I3- and I2 groups with I···I contacts of 3.468(1) Å. Crystal data; compound 1: orthorhombic; space group Pna21; a = 24.750(3), b = 11.521(3), c = 11.348(3) Å, V = 3236(1) Å3; Z = 4; dc = 2.691 g cm-3; μ (Mo-Kα) = 61.35 cm-1; R = 0.046 (Rw = 0.049) for 1827 reflections having F02 > 3σ(F02); compound 2: monoclinic; space group P21/m; a = 15.006(3), b =9.647(3), c = 8.986(3) Å, β = 95.76(2)°; V = 1294.3(6) Å3; Z = 2; dc = 2.830 g cm-3; μ (Mo-Kα) = 71.97 cm-1; R = 0.042 (Rw = 0.051) for 1509 reflections having F02 > 3σ(F02).

Domaines: Chimie de coordination

Fausto Calderazzo, Rinaldo Poli, Pier Francesco Zanazzi. Oxidation of η6-arene Complexes of Group VI Metals. Part 4. Molybdenum(II)-arene-carbonyl Compounds Containing Polyiodides. Gazzetta Chimica Italiana, 1988, 118, pp.595-601. ⟨hal-03574269⟩