Structural comparison to the molybdenum site of nitrogenase. Synthesis and crystal structure of binuclear oxomolybdenum(V) complex with both o ‐mercaptophenolate and alkoxide ligands

Complex ( n ‐Bu 4 N)[Mo 2 O 2 (OMe)(mp) 3 ] [1, mp = ( o ‐OC 6 H 4 S) 2 −] was synthesized by the reaction of MoOCl 3 (THF) 2 and Na 2 mp in EtOH and crystallized in monoclinic space group P 2 1 / n with crystal data: a = 13.910(3), b = 23.554(3), c =12.558(2) Å, β = 105.20(2) ˙ . Z = 4, D o = 1.455g/ cm 3 , final R = 0.077 for 5325 reflections [ I >3s̀(I)]. The two [Mo(O)mp]+ moieties are bridged by one 1,2‐bidentate ligand mp 2− with exceedingly small bite angle (69.0 ˙ ) and bite distance · (2.70Å) and by a methoxy group. The structure can be interpreted as two distorted octahedra around the Mo atoms sharing a face. Attempts have been made to provide structural informations for the syntheses of modelling compounds of FeMoco by comparing the Mo—O and Mo—S bond distances of o ‐mercaptophenolate ligated compounds to those of the molybdenum site of nitrogenase.