Three new types of transition metal carboranylamidinate complexes

Abstract

Three new types of transition metal carboranylamidinate complexes are reported. The tetranuclear Mn(II) complex Mn₄Cl₆[(o-C₂B₁₀H₁₀)C(NⁱPr)(NHⁱPr)]₂(THF)₄·THF (2) was prepared by treatment of anhydrous MnCl₂ with Li[(o-C₂B₁₀H₁₀)C(NⁱPr)(NHⁱPr)] (Li[HL^iPr]) in THF, while the analogous reaction with FeCl₂ afforded ionic [Li(DME)₃][FeCl₂{(o-C₂B₁₀H₁₀)C(NⁱPr)(NHⁱPr)}] (3). The dinuclear Mo(II) complex Mo₂[(o-C₂B₁₀H₁₀)C(NⁱPr)(NHⁱPr)]₂(OAc)₂·2THF (4), obtained from Mo₂(OAc)₄ and 2 equiv. of Li[HL^iPr], represents the first example of a M–M multiple bond stabilized by carboranylamidinate ligands. All title compounds were structurally characterized by single-crystal X-ray diffraction. The M–M bonding in compound 4 has been further elucidated through Complete Active Space Self Consistent Field (CASSCF) calculations.