An "intermediate spin" nickel hydride complex stemming from delocalized Ni2(μ-H)2 bonding.
An "intermediate spin" nickel hydride complex stemming from delocalized Ni2(μ-H)2 bonding.
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源自离域 Ni2(μ-H)2 键合的“中间自旋”氢化镍络合物。
DOI：
10.1021/ja507342a
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发表时间：
2014
影响因子：
15
通讯作者：
Berry,JohnF
中科院分区：
文献类型：
--
作者：
Yao,ShuA;Corcos,AmandaR;Infante,Ivan;Hillard,ElizabethA;Clérac,Rodolphe;Berry,JohnF
发现氢化镍配合物[Cp′Ni（μ-H）]2（1，Cp′ = 1，2，3，4-四异丙基甲基）具有非常短的Ni-Ni距离，为2.28638（3）<$.变温和磁场测量表明，1的三重基态具有+90 K（63 cm-1）的大的零场分裂。电子结构计算（DFT和CASSCF/CASPT 2）解释了这种基态是由两个近简并的Ni-Ni π* 轨道的半占据引起的。
The nickel hydride complex [Cp′Ni(μ-H)]2(1, Cp′ = 1,2,3,4-tetraisopropylcyclopentadienyl) is found to have a strikingly short Ni–Ni distance of 2.28638(3) Å. Variable temperature and field magnetic measurements indicate an unexpected triplet ground state for1with a large zero-field splitting of +90 K (63 cm–1). Electronic structure calculations (DFT and CASSCF/CASPT2) explain this ground state as arising from half occupation of two nearly degenerate Ni–Ni π* orbitals.