Synthesis and Structures of Mono‐ and Dinuclear Molybdenum Complexes with Reduced α‐Diimine Ligands. Issue 35 (9th November 2016) - Zhao, Yanxia
Abstract : The mononuclear molybdenum complex [Mo( H L)2 ] (1 ), Mo–Mo single‐bond compound [ H LClMo(µ‐Cl)3 Mo H LCl] [2 ; Mo–Mo 2.832(7) Å], and Mo≡Mo triple‐bond compounds [Mo2 Cl2 (µ‐ H L)2 ] [3 ; Mo–Mo 2.194(6) Å] and [Mo2 Cl2 (µ‐Cl)(µ‐ H L)Cl2 Na(THF)3 ] [4 ; Mo–Mo 2.167(2) Å] have been synthesized by the reaction of H L { H L = [(2, 6‐ i Pr2 C6 H3 )NCH]2 } with 0.5, 1, and 2 equiv. of MoCl5 and different amounts of Na metal. In the single‐bond compound2, the α‐diimine ligand H L displays the normal chelating coordination mode. In contrast, the triple‐bond compounds3 and4 feature the less common bridging mode of α‐diimine ligands. Complexes1 –4 have been characterized by X‐ray diffraction, 1 H and 13 C NMR, IR spectroscopy, elemental analysis, and their electronic structures were studied by EPR and DFT computations. Abstract : A series of molybdenum complexes, including two Mo≡Mo triple‐bond, one Mo–Mo single‐bond, and one mononuclear compound, with dianionic α‐diimine ligands H L 2– and different oxidation states of molybdenum centers (+3, +4, or +5), have been synthesized and characterized.