Transition-Metal Chemistry of Alkaline-Earth Elements: The Trisbenzene Complexes M(Bz)(3) (M=Sr, Ba)
Transition-Metal Chemistry of Alkaline-Earth Elements: The Trisbenzene Complexes M(Bz)(3) (M=Sr, Ba)
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碱土元素的过渡金属化学：三苯配合物 M(Bz)(3) (M=Sr, Ba)
DOI：
10.1002/anie.201908572
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发表时间：
2019
期刊：
影响因子：
--
通讯作者：
Frenking Gernot
中科院分区：
文献类型：
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作者：
Wang Qian;Pan Sudip;Wu Yan-Bo;Deng Guohai;Bian Jian-Hong;Wang Guanjun;Zhao Lili;Zhou Mingfei;Frenking Gernot
本文报道了锶钡三苯配合物M(Bz)3（M=Sr, Ba）在低温Ne基体中的合成和光谱鉴定。这两种配合物都具有ad3对称结构，包括三个等效的η - 6键苯配体和一个闭合壳层单重态电子基态。电子结构分析表明，配合物具有典型过渡金属化合物的金属-配体键。这种化学键可以用苯配体的π* MOs弱给给M的空位（n−1）d AO和M的占位（n−1）d AO强反给给到苯配体的空位π* MOs来解释。这些20电子配合物中的金属有18个有效价电子，因此，如果只计算金属-配体成键电子，则满足18电子规则。结果表明，较重的碱土原子表现出过渡金属的全键情景。
We report the synthesis and spectroscopic identification of the trisbenzene complexes of strontium and barium M(Bz)3(M=Sr, Ba) in low‐temperature Ne matrix. Both complexes are characterized by aD3symmetric structure involving three equivalent η6‐bound benzene ligands and a closed‐shell singlet electronic ground state. The analysis of the electronic structure shows that the complexes exhibit metal–ligand bonds that are typical for transition metal compounds. The chemical bonds can be explained in terms of weak donation from the π MOs of benzene ligands into the vacant (n−1)d AOs of M and strong backdonation from the occupied (n−1)d AO of M into vacant π* MOs of benzene ligands. The metals in these 20‐electron complexes have 18 effective valence electrons, and, thus, fulfill the 18‐electron rule if only the metal–ligand bonding electrons are counted. The results suggest that the heavier alkaline earth atoms exhibit the full bonding scenario of transition metals.