Oxygen abstraction from tetrahydrofuran by molybdenum-iodide complexes. X-ray molecular structure of [Mo2(μ-O)(μ-I)(μ-O2CCH3)I2(THF)4][MoOI4(THF)] (THF = tetrahydrofuran)

F. Albert Cotton (1) , Rinaldo Poli (1)

1 Texas A&M University [College Station]

The interaction between Mo2(O2CCH3)4, Me3SiI and I2 in THF resulted in oxygen abstraction from the solvent and formation of [Mo2(μ-O)(μ-I)(μ-O2CCH3) I2(THF)4]+[MoOI4(THF)]− and I−(CH2)4−I. The molybdenum complex has been characterized by X-ray diffractometry. Crystal data: triclinic, space group P1, a = 13.827(3) Å; b = 15.803(7) Å; c = 9.950(3) Å; α = 93.34(4)°; β = 102.40(2)°; γ = 90.09(2)°; V = 2120(2) Å3; Z = 2; dcalc = 2.559 g cm−3; R = 0.0476 (Rw = 0.0613) for 370 parameters and 3938 data with F02 > 3σ(F02). The metal-metal distance in the cation is 2.527(2) Å and indicates a strong interaction. The magnetic behavior is consistent with the assignment of one unpaired electron to the Mo27+ core of the cation and one to the d1 Mo(V) center of the anion. The interaction between Mo(CO)6 and I2 in THF also results in the formation of 1,4-diiodobutane.

Domaines: Chimie de coordination; Cristallographie

F. Albert Cotton, Rinaldo Poli. Oxygen abstraction from tetrahydrofuran by molybdenum-iodide complexes. X-ray molecular structure of [Mo2(μ-O)(μ-I)(μ-O2CCH3)I2(THF)4][MoOI4(THF)] (THF = tetrahydrofuran). Polyhedron, 1987, 6 (12), pp.2181-2186. ⟨10.1016/S0277-5387(00)84284-9⟩. ⟨hal-03544677⟩