Amine-oxide-mediated reactions of Re2(CO)10 with phenol and aliphatic alcohols: The formation of Re3(CO)14(μ-H) and a hydroxo-methoxo trirhenium aggregate [Me3NH]+[Re3(CO)9(μ-OH)2(μ-OMe)(μ3-OMe)]-

Article abstract of DOI:10.1016/S0022-328X(97)00207-6

Oxidative decarbonylation of Re₂(CO)₁₀ by Me₃NO in a mixture of THF and phenol resulted in Re₃(CO)₁₄(μ-H), 1, and [Me₃NH]⁺[Re₂(CO)₆(μ-OPh)₃]^-, 2, in 30 and 17% yields respectively. In the analogous reaction in THF-MeOH mixture, a trinuclear complex, [Me₃NH]⁺[Re₃(CO)₉(μ-OH)₂(μ-OMe)(μ₃-OMe)]^-, 3, was isolated instead. The structure of 3 was determined by single-crystal X-ray diffraction analysis: orthorhombic, space group Ama2, a = 14.022(2), b = 18.003(5), c = 9.601(2) A, final R = 0.031 for 958 reflections. The anion contains a Re₃ triangle edge-bridged by one methoxy and two hydroxy ligands and capped by a methoxy group. No formal Re-Re bond (Re ... Re 3.423 and 3.439 A) is envisaged. Possible mechanisms for the formation of 1, 2 and 3 are proposed.