Theoretical and Experimental Characterization of Cr−L Multiple Bonds (L = O, N, and C)
Theoretical and Experimental Characterization of Cr−L Multiple Bonds (L = O, N, and C)
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DOI：
10.1021/jp001130x
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发表时间：
2000-10
影响因子：
2.9
通讯作者：
Chih‐Chieh Wang;†. A. T. Tang;Yu Wang
中科院分区：
文献类型：
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作者：
Chih‐Chieh Wang;†. A. T. Tang;Yu Wang
对一系列Cr-配合物[(CO)4(Cl)Cr(I)(CPh)] 1进行了Cr−L （L = O， N， C）多键键表征的实验与理论结合研究；[Cr (V) (N) (bpb) 2,和[Cr (V) (N-t-Bu) (bpb) (Cl)] 3,在[bpb2 - =(1,以叔(pyridine-2-carboxamido)苯)];和[(TPPOMe)Cr(IV)O] 4，其中[TPPOMe =（5,10,15,20-对甲氧基苯基）卟啉]。用精确单晶x射线衍射对化合物1和2进行了表征。基于自然成键轨道（NBO）分析和费米空穴函数，给出了Cr - Ccarbyne、Cr - Nnitrido、Cr - Nimido和Cr - Ooxo键的详细描述。所有这些多键的成键特征本质上是由一个σ键和两个π键组成的三键特征。Cr−L多键的σ特征是高度极化的，电子密度向L （O， N， C）配体方向强烈极化。Cr−L多键的π特征取决于L配体的性质，即电子密度向Cr和L的方向极化。
A combined experimental and theoretical study on the bond characterization of Cr−L (L = O, N, C) multiple bonds is applied to a series of Cr-complexes: [(CO)4(Cl)Cr(I)(CPh)] 1; [Cr(V)(N)(bpb)] 2, and [Cr(V)(N-t-Bu)(bpb)(Cl)] 3, where [bpb2- = (1,2-bis(pyridine-2-carboxamido)benzene)]; and [(TPPOMe)Cr(IV)O] 4, where [TPPOMe = (5,10,15,20-p-methoxyphenyl)porphyrin)]. Compounds 1 and 2 were investigated by accurate single-crystal X-ray diffraction. Detailed descriptions of Cr−Ccarbyne, Cr−Nnitrido, Cr−Nimido, and Cr−Ooxo bonds will be given based on the natural bonding orbital (NBO) analyses and Fermi hole function. The bonding feature of all these multiple bonds is essentially a triple bond character consisting of one σ and two π bonds. The σ character of the Cr−L multiple bonds is a highly polarized one with the electron density strongly polarized toward L (O, N, C) ligands. The π character of the Cr−L multiple bonds depends on the nature of L ligand, i.e., with electron density polarized toward the Cr an...