TY - JOUR
T1 - Preparation of Heterobimetallic Cuboidal Clusters[M3NiS4(H2O)10]4+ (M=Mo,W) and their Reactivity towards Co.
AU - Hjortkjær, Jes
PY - 1996
Y1 - 1996
N2 - A new substantially improved synthesis of [{W3NiS4(H2O)9} 2](pts)8·20H2O (pts=p-toluenesulfonate) based on reaction of [W3S4]4+ with nickel in 2 M HCl is reported. The reaction proceeded within 2 h and an isolated yield of >95% based on [W3S4]4+ was obtained. Similary, [Mo3NiS4(H2O)10](Pts) 4·-7H2O was prepared by a novel procedure based on the reduction of MoS42- with excess Ni at 70°C, followed by oxidation with air to obtain [Mo3S4]4+ and subsequently reflux under N2 to yield [Mo3NiS4]4+. This procedure allowed a one-pot synthesis of [Mo3S4]4+ and/or [Mo3NiS4]4+ from tetrathiomolybdate(VI). Further-more, a new method was developed for the quantitative isolation of [Mo3NiS4(H2O)10](Pts) 4·7H2O and [{W3NiS4(H2O)9} 2](pts)8·20H2O. This is based on chromatographic separation by elution with 3.5 M trifluoroacetic acid (CF3COOH), and succesive dilutions and evaporations. The [M3NiS4(H2O)10]4+ (M=Mo, W) clusters are potential candidates for homogeneous hydrodesulfurisation catalysts and, for comparison with heterogeneous catalysts, their reactivity towards carbon monoxide was studied. UV-VIS absorption, IR and 13C NMR spectroscopy revealed that CO was reversibly coordinated to Ni in the very airsensitive [M3NiS4]4+ clusters. Upon coordination of CO the clusters could be handled in air for long periods without oxidation.
AB - A new substantially improved synthesis of [{W3NiS4(H2O)9} 2](pts)8·20H2O (pts=p-toluenesulfonate) based on reaction of [W3S4]4+ with nickel in 2 M HCl is reported. The reaction proceeded within 2 h and an isolated yield of >95% based on [W3S4]4+ was obtained. Similary, [Mo3NiS4(H2O)10](Pts) 4·-7H2O was prepared by a novel procedure based on the reduction of MoS42- with excess Ni at 70°C, followed by oxidation with air to obtain [Mo3S4]4+ and subsequently reflux under N2 to yield [Mo3NiS4]4+. This procedure allowed a one-pot synthesis of [Mo3S4]4+ and/or [Mo3NiS4]4+ from tetrathiomolybdate(VI). Further-more, a new method was developed for the quantitative isolation of [Mo3NiS4(H2O)10](Pts) 4·7H2O and [{W3NiS4(H2O)9} 2](pts)8·20H2O. This is based on chromatographic separation by elution with 3.5 M trifluoroacetic acid (CF3COOH), and succesive dilutions and evaporations. The [M3NiS4(H2O)10]4+ (M=Mo, W) clusters are potential candidates for homogeneous hydrodesulfurisation catalysts and, for comparison with heterogeneous catalysts, their reactivity towards carbon monoxide was studied. UV-VIS absorption, IR and 13C NMR spectroscopy revealed that CO was reversibly coordinated to Ni in the very airsensitive [M3NiS4]4+ clusters. Upon coordination of CO the clusters could be handled in air for long periods without oxidation.
U2 - 10.3891/acta.chem.scand.50-0871
DO - 10.3891/acta.chem.scand.50-0871
M3 - Journal article
SN - 0904-213X
VL - 50
SP - 871
EP - 874
JO - Acta Chemica Scandinavica
JF - Acta Chemica Scandinavica
IS - 10
ER -