Amine-oxide-mediated reactions of Re-2(CO)(10) with phenol and aliphatic alcohols: The formation of Re-3(CO)(14)(mu-H) and a hydroxo-methoxo trirhenium aggregate [Me3NH](+)[Re-3(CO)(9)(mu-OH)(2)(mu-OMe)(mu(3)-OMe)](-)

Oxidative decarbonylation of Re-2(CO)(10) by Me3NO in a mixture of THF and phenol resulted in Re-3(CO)(14)(mu-H), 1, and [Me3NH](+)[Re-2(CO)(6)(mu-OPh)(3)](-), 2, in 30 and 17% yields respectively. In the analogous reaction in THF-MeOH mixture, a trinuclear complex, [Me3NH](+)[Re-3(CO)(9)(mu-OH)(2)(mu-OMe)(mu(3)-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) Angstrom, final R = 0.031 for 958 reflections. The anion contains a Re-3 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 Angstrom) is envisaged. Possible mechanisms for the formation of 1, 2 and 3 are proposed. (C) 1997 Elsevier Science S.A.