Structural distortion of the TpCo-L fragment (Tp=tris(pyrazolyl)borate). Analysis by X-ray diffraction and density functional theory
Structural distortion of the TpCo-L fragment (Tp=tris(pyrazolyl)borate). Analysis by X-ray diffraction and density functional theory
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DOI：
10.1021/ja9523101
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发表时间：
1996-02-21
影响因子：
15
通讯作者：
Theopold, KH
中科院分区：
文献类型：
--
作者：
Detrich, JL;Konecny, R;Theopold, KH
配位不饱和[（Tp（Np）CO）（2）（mu-N-2）]和Tp（Np）Co（CO）的晶体结构显示出“弯曲"分子，其中第四配体（N-2，CO）从TpCo部分的伪三重轴弯曲27-38度。Tp（t-Bu，Me）Co（CO）的镁还原产生[Tp（t-Bu，Me）Co（mu-CO）]Mg-2（THF）（4），其结构也被表征;还原的羰基是“线性的”。采用扩展Huckel理论（EHT）和密度泛函理论（DFT）对TpCo-L片段（L = CO（Co-1，d（8）），COLi（Co-0，d（9）），I（Co-II，d（7）的电子结构和结构偏好进行了理论分析.实际和理论结构测定结果吻合良好。根据这些结果，我们认为d（8）TpCo-L配合物和等电子CpM-L配合物都具有“弯曲"结构.
The crystal structures of coordinatively unsaturated [(Tp(Np)CO)(2)(mu-N-2)] and Tp(Np)Co(CO) show ''bent'' molecules, in which the fourth ligand (N-2, CO) is bent away from the pseudo-threefold axis of the TpCo-moiety by 27-38 degrees. Magnesium reduction of Tp(t-Bu,Me)Co(CO) yielded [Tp(t-Bu,Me)Co(mu-CO)]Mg-2(THF)(4) which was also structurally characterized; the reduced carbonyl is ''linear''. Extended Huckel theory (EHT) and density functional theory (DFT) have been used to analyze the electronic structures and structural preferences of the TpCo-L fragment with L = CO (Co-1, d(8)), COLi (Co-0, d(9)), and I (Co-II, d(7)). The actual and theoretical structure determinations were in good agreement. Based on these results we suggest that d(8) TpCo-L complexes and, by analogy, isoelectronic CpM-L complexes assume ''bent'' structures.