Inorganic Chemistry, Vol.33, No.16, 3438-3441, 1994
Isovalent and Mixed-Valent Dinuclear Mu-Oxo and Mu-Oxo Mu-Disulfido Complexes of Molybdenum(V) and Molybdenum(VI)
Reactions of {HB(Me2pz)3}Mo(VI)O2Br with aqueous ammonia solution or Bun4NSH in dry dichloromethane produce the isovalent dinuclear complexes [{HB(Me2PZ)3}Mo(VI)O2]2(mu-O) (1) and [{HB(Me2pz)3}Mo(V)O]2(mu-O)(mu-S2) (2), respectively. Reaction of {HB(Me2PZ)3}Mo(VI)O2(SPh) and PPh3 in dry toluene results in the formation of isovalent [{HB(Me2PZ)3}Mo(V)O(SPh)]2(mu-O) (3) via a comproportionation reaction involving Mo(VI) and Mo(IV) centers. Mixed-valent {HB(Me2PZ)3}Mo(VI)O2(mu-O)Mo(V)OX{HB(Me2PZ)3} (X = Br (4), SPh (5)) form upon reaction of {HB(Me2PZ)3}Mo(VI)O2Br and PhSH/Et3N in dry dichloromethane. Reliable syntheses and infrared, H-1 NMR (EPR), and UV-visible spectroscopic and mass spectrometric data for compounds 1-5 are reported.