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

journal contribution
posted on 2023-06-07, 22:53 authored by Sian C Davies, David L Hughes, Raymond L Richards, J Roger Sanders
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)33-] together with a small amount of dark red, diamagnetic [{Mo(NS3)}2(µ-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)]BF49 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(µ-Br)Br(CO)4}2] and [WI2(CO)3(MeCN)2] gave the poorly soluble, diamagnetic complexes [{M(NS3)}2{µ-SCH2CH2N(CH2CH2SH)2-S}2] (M = Mo 11 or W 12) whose structures have been established by determination of the crystal structure of 12.


Publication status

  • Published


Journal of the Chemical Society, Dalton Transactions




RSC Publishing



Page range

719 - 725



Department affiliated with

  • Chemistry Publications

Full text available

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Peer reviewed?

  • Yes

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