SYNTHESES, PROPERTIES AND X-RAY CRYSTAL STRUCTURES OF HEXANUCLEAR COBALT-CHALCOGEN CLUSTERS CO6S8(PPH3)6 AND CO6SE8(PPH3)6.THF
作者： Maochun Hong , Zhiying Huang , Xinjian Lei , Guowei Wei , Beisheng Kang
DOI: 10.1016/S0277-5387(00)86910-7
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摘要: Abstract The reaction of Na2Xx (X = S or Se) with CoBr2 and triphenylphosphine in DMF gave rise to the clusters Co6X8(PPh3)6 [X (I), X Se (II)] high yields. molecular structures I II have been determined by single-crystal X-ray diffraction. Both were solved direct methods refined full-matrix least-squares techniques converge R 0.053 for 0.048 on basis 5488 8175 reflections > 3σ(I), respectively. two are isostructural inner core consisting a slightly distorted Co6 octahedron. CoCo distances fall ranges 2.848–2.894 A 2.955–3.037 II. Electrochemistry dichloromethane shows electron-transfer sequence I: Co6S8(PPh3)6⇌[Co6S8(PPh3)6]+ II: Co6Se8(PPh3)6⇌[CO6Se8(PPh3)6]+⇌[Co6Se8 (PPh3)6]2+.
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