Theoretical Study on the Tropos Nature of the BIPHEP−Pd(II)/DABN and DPEN Complexes: PIO Analysis of Phosphine−Pd(II) Interaction and Trans Influence†
Theoretical Study on the Tropos Nature of the BIPHEP−Pd(II)/DABN and DPEN Complexes: PIO Analysis of Phosphine−Pd(II) Interaction and Trans Influence†
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DOI：
10.1021/om050249v
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发表时间：
2005-08
期刊：
影响因子：
2.8
通讯作者：
M. Yamanaka;K. Mikami
中科院分区：
文献类型：
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作者：
M. Yamanaka;K. Mikami
通过B3LYP方法和配对相互作用轨道（PIO）分析，从理论上研究了手性柔性（对偶）联苯膦（BIPHEP）配体与二苯乙二胺（DPEN）或二氨基萘（DABN）结合的Pd（II）配合物的轴向手性控制能力。采用简单Pd（II）复合物模型PR3Pd（II）和PR3Pd(II)NMe3 (R = H, Ph)，探讨了磷化氢- Pd（II）部分的键相互作用和NMe3配位的反式影响。PPh3Pd（II）配合物的PIO分析表明，在NMe3配位作用下，PPh3Pd（II）空位轨道的σ-给度被放大，P−C σ*轨道的π-背给度得以保持。在BIPHEP−Pd（II）模型中也观察到简单模型的类似反影响趋势。BIPHEP−Pd(II)/DPEN具有强烈的atropos性质的原因可能是与Pd 4dxz和4dx2-y2的σ-相互作用增强，而强捐赠DP的协调作用则相对放大了σ-相互作用。
The facility of axial chirality control of the Pd(II) complex bearing a chirally flexible (tropos) biphenylphosphine (BIPHEP) ligand with combination of diphenylethylenediamine (DPEN) or diaminobinaphthyl (DABN) was theoretically studied by the B3LYP methods and the paired interacting orbital (PIO) analysis. The simple Pd(II) complex models PR3Pd(II) and PR3Pd(II)NMe3 (R = H, Ph), were also employed to probe the bonding interaction of the phosphine−Pd(II) moiety and the trans influence of NMe3 coordination. The PIO analysis of the PPh3Pd(II) complex indicates that the σ-donation to the vacant Pd 4d orbital is amplified, keeping the π-back-donation to the P−C σ* orbital by NMe3 coordination. A similar tendency of the trans influence of the simple model was also observed in the BIPHEP−Pd(II) models. The origin of the strong atropos nature of BIPHEP−Pd(II)/DPEN can be caused by enhancement of the σ-interactions with Pd 4dxz and 4dx2-y2, which are relatively amplified by coordination of a strongly donative DP...