C≡N and N≡O Bond Cleavages of Acetonitrile and Nitrosyl Ligands at a Dimolybdenum Center to Render Ethylidyne and Acetamidinate Ligands.

Abstract

Extended reduction of [Mo2Cp2(μ-Cl)(μ-PtBu2)(NO)2] (1) with Na(Hg) in acetonitrile (MeCN) at room temperature resulted in an unprecedented full cleavage of the C≡N bond of a coordinated MeCN molecule to yield the vinylidene derivative Na[Mo2Cp2(μ-PtBu2)(μ-CCH2)(NO)2], which upon protonation with (NH4)PF6 gave the ethylidyne complex [Mo2Cp2(μ-PtBu2)(μ-CMe)(NO)2] [Mo1-Mo2 = 2.9218(2) Å] in a selective and reversible way. Controlled reduction of 1 at 273 K yielded instead, after protonation, the 30-electron acetamidinate complex [Mo2Cp2(μ-PtBu2)(μ-κN:κN'-HNCMeNH)(μ-NO)]PF6 [Mo1-Mo2 = 2.603(2) Å], in a process thought to stem from the paramagnetic MeCN-bridged intermediate [Mo2Cp2(μ-PtBu2)(μ-NCMe)(NO)2], followed by a complex sequence of elementary steps including cleavage of the N≡O bond of a nitrosyl ligand.