Turning a New Leaf on Metal-TMC Chemistry: NiII(TMC) Acetylides

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• 作者：Sarah F. Tyler ; Sean N. Natoli ; Bess Vlaisavljevich ; Phillip E. Fanwick ; Tong Ren
• 刊名：Inorganic Chemistry
• 出版年：2015
• 出版时间：October 19, 2015
• 年：2015
• 卷：54
• 期：20
• 页码：10058-10064
• 全文大小：462K
• ISSN：1520-510X

文摘

Novel [Ni(TMC)C鈮Y]⁺-type compounds 1鈥?b>4 [TMC = 1,4,8,11-tetramethyl-1,4,8,11-tetraazacyclotetradecane; Y = SiMe₃ (1), SiⁱPr₃ (2), Ph (3), and C₂H (4)] have been synthesized and characterized. Single-crystal X-ray diffraction studies revealed that these compounds adopt a distorted square-pyramidal geometry, with the acetylide ligand occupying the apical position and a RSRS isomer for the TMC ligand. The room temperature magnetic properties of 1鈥?b>4 are consistent with an S = 1 ground state, as corroborated by CASSCF and density functional theory calculations, which indicate that the singly occupied molecular orbitals are d_z² and d_x²鈥?i>y².