An 鈥淚ntermediate Spin鈥?Nickel Hydride Complex Stemming from Delocalized Ni2(渭-H)2 Bonding

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• 作者：Shu A. Yao ; Amanda R. Corcos ; Ivan Infante ; Elizabeth A. Hillard ; Rodolphe Cl茅rac ; John F. Berry
• 刊名：Journal of the American Chemical Society
• 出版年：2014
• 出版时间：October 1, 2014
• 年：2014
• 卷：136
• 期：39
• 页码：13538-13541
• 全文大小：307K
• ISSN：1520-5126

文摘

The nickel hydride complex [Cp鈥睳i(渭-H)]₂ (1, Cp鈥?= 1,2,3,4-tetraisopropylcyclopentadienyl) is found to have a strikingly short Ni鈥揘i distance of 2.28638(3) 脜. Variable temperature and field magnetic measurements indicate an unexpected triplet ground state for 1 with a large zero-field splitting of +90 K (63 cm^鈥?). Electronic structure calculations (DFT and CASSCF/CASPT2) explain this ground state as arising from half occupation of two nearly degenerate Ni鈥揘i 蟺* orbitals.