Triply bridged (O,O′,S)-binuclear oxomolybdenum(V) complexes containing o-mercaptophenol ligands

Abstract Complexes [A][Mo 2 O 2 (μ-O)mp 3 Na(EtOH) 3 ] (A = Et 4 N (1a); A = nBu 4 N (1b)) and (n-Bu 4 N) [Mo 2 O 2 (μ-OEt)mp 3 ] (2) have been obtained by the reaction of MoOCl 3 (THF) 2 and Na 2 mp (H 2 mp = o -mercaptophenol) in appropriate solvents. Both (1b) and (2) crystallize in monoclinic space group P2 1 /n. Cell parameters for (1b): a = 12.776(3), b = 14.154(5), c = 26.281(7) A, β = 95.50(2)°, V = 4730.5 A 3 , Z = 4, D calc = 1.427 g/cm 3 ; for (2): a = 12.617(5), b = 23.817(18), c = 14.228(7) A, β = 105.79(4)°, V = 4114.1 A 3 , Z = 4, D calc = 1.427 g/cm 3 . The structures were solved by direct methods from 3348 (1b) or 1583 (2) unique reflections with I > 3σ (I) to final convergence factors of R(R w ) 0.070(0.070) for (1b) and 0.090(0.099) for (2). The two [Mo(O)mp] + units are triply bridged by one doubly bridging mp 2− ligand with exceedingly small bite angles (68.85°) and bite distances (2.70 A) and an inorganic oxygen atom for (1b) or an ethoxy group for (2). The molybdenum(V) atoms are in an environment of O 4 S 2 , forming a distorted octahedron with the terminal oxo groups cis to each other. Information concerning the possible origin of oxygen atoms in MoFepr is derived from the structural data of these two complexes. 1 H NMR and CV measurements were also studied.