A Novel Ligand Modification and Diamond-core Molybdenum(IV) 2,6-Bis(2,2-diphenyl-2-thioethyl)pyridinate(2-) Complex

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• 作者：Craig Gourlay ; Christian J. Doonan ; Jonathan M. White ; Charles G. Young
• 刊名：Inorganic Chemistry
• 出版年：2008
• 出版时间：December 1, 2008
• 年：2008
• 卷：47
• 期：23
• 页码：11166-11170
• 全文大小：184K
• 年卷期：v.47,no.23(December 1, 2008)
• ISSN：1520-510X

文摘

The reaction of Mo^VIO₂(L-NS₂) [L-NS₂ = 2,6-bis(2,2-diphenyl-2-thioethyl)pyridinate(2-)] or Mo^V₂O₃(L-NS₂)₂ with excess PPh₃ in N,N-dimethylformamide at 70 °C results in the formation of gray-green (L-NOS)Mo^IV(μ-O)(μ-S)Mo^IV(L-NS₂) [L-NOS = 2-(2,2-diphenyl-2-thioethyl)-6-(2,2-diphenyl-2-oxoethyl)pyridinate(2-)] (1). The crystal structure of 1 revealed a dinuclear complex comprised of two trigonal bipyramidal Mo centers bridged along an axial−equatorial edge (the μ-O-μ-S vector) such that the Mo−N bonds are trans to the bridging atoms and are anti with respect to the Mo−Mo bond (d(Mo−Mo) = 2.5535(5) Å); the remaining coordination sites are occupied by the S- and O-donor atoms of the L-NOS and L-NS₂ ligands. The diamond core is asymmetric, with Mo(1/2)−O(1) distances of 1.845(2) and 2.009(2) Å and Mo(1/2)−S(1) distances of 2.374(1) and 2.230(1) Å. Compound 1 is unique in possessing a planar, diamond-core unit devoid of terminal oxo ligation and a new tridentate L-NOS ligand formed via a novel intramolecular modification of the original L-NS₂ ligand.