Molybdenum and tungsten complexes of the N(CH2CH2S)33- (NS3) ligand with oxide, sulfide, diazenide, hydrazide and nitrosyl co-ligands

Reaction of [MoO2(acac)(2)] with N(CH2CH2SH)(3) in CH2Cl2 gave an insoluble, red, diamagnetic complex formulated as [{MoO(NS3)}(2)] 1 [NS3 = ;N(CH2CH2S)(3)(3-)] together with a small amount of dark red, diamagnetic [{Mo(NS3)}(2)(mu-S)] 2. The linear, sulfur-bridged structure of 2 was confirmed by a crystal structure determination. With NH2NHR (R = Me or Ph) in CH2Cl2, 1 gave soluble, red, diamagnetic diazenides [Mo(NS3)(N2R)] (R = Me 3 or Ph 4) whereas with N2H4 it gave a dark brown, insoluble compound formulated as [{Mo(NS3)(N2H)}(n)] 5. The crystal structures of 3 and 4 have been obtained. Both 3 and 4 react with mineral acids HX (X = BF4 or Cl) in CH2Cl2 to give the yellow-brown, diamagnetic hydrazides [Mo(NS3)(N2HR)]X (6, R = Me, X = BF4; 7, R =Me, X = Cl; 8, R = Ph, X = BF4), which deprotonate in more basic solvents to regenerate the parent complexes. Compound 3 reacted with [Me3O]BF4 to give yellow, diamagnetic [Mo(NS3)(N2Me2)]BF4 9 and with NO to give yellow, diamagnetic [Mo(NS3)(NO)] 10, whose crystal structure shows it to have a linear MoNO system. Reaction of N(CH2CH2SH)(3) with [{Mo(mu-Br)Br(CO)(4)}(2)] and [WI2(CO)(3)(MeCN)(2)] gave the poorly soluble, diamagnetic complexes [{M(NS3)}(2){mu-SCH2CH2N(CH2CH2SH)(2)-S}(2)] (M = Mo 11 or W 12) whose structures have been established by determination of the crystal structure of 12.