Synthesis and Structures of Mono‐ and Dinuclear Molybdenum Complexes with Reduced α‐Diimine Ligands

Abstract

The mononuclear molybdenum complex [Mo(HL)2] (1), Mo–Mo single‐bond compound [HLClMo(µ‐Cl)3MoHLCl] [2; Mo–Mo 2.832(7) Å], and Mo≡Mo triple‐bond compounds [Mo2Cl2(µ‐HL)2] [3; Mo–Mo 2.194(6) Å] and [Mo2Cl2(µ‐Cl)(µ‐HL)Cl2Na(THF)3] [4; Mo–Mo 2.167(2) Å] have been synthesized by the reaction of HL {HL = [(2,6‐iPr2C6H3)NCH]2} with 0.5, 1, and 2 equiv. of MoCl5 and different amounts of Na metal. In the single‐bond compound 2, the α‐diimine ligand HL displays the normal chelating coordination mode. In contrast, the triple‐bond compounds 3 and 4 feature the less common bridging mode of α‐diimine ligands. Complexes 1–4 have been characterized by X‐ray diffraction, 1H and 13C NMR, IR spectroscopy, elemental analysis, and their electronic structures were studied by EPR and DFT computations.