(NH)-Phosphanylamido-and (PH)-Phosphoraneiminato Transition-Metal Complexes: Syntheses, Structures, and Computational Studies

Mochael Raab; Andreas Sundermann; Gerold Schick; Armin Loew; Martin Nieger; Wolfgang W.Schoeller; Edgar Niecke

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(NH)-Phosphanylamido-and (PH)-Phosphoraneiminato Transition-Metal Complexes: Syntheses, Structures, and Computational Studies

机译：（NH）-磷酰胺基和（PH）-磷亚胺基过渡金属配合物：合成，结构和计算研究

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Reactions of aminobis(diorganylamino)phosphanes (R_2N)_2PNH_2 (R = iPr(a), Cy(b)) with Cp_2MCl_2 (M = Ti, Zr, Hf), CpTiCl_3, and TiCl_4 lead to the formation of the transition-metal complexes (R_2N)_2PN(H)MCp_2Cl (M = Ti(1b), Zr(2a, b), Hf(3a, b)) (R_2N)_2P(H)NTiCpCl_2 (8a, b), and (R_2N)_2P(H)NTiCl_3 (10a, b), respectively. The inlfuence of electronic effects of the metal fragment on the resulting equilibrium between the (NH)-phospanylamido and the tautomeric (PH)-iminophosphorane form is presented in detail. Computational studies unambiguously confirm the experimental results. The molecular structures of 2a, 3a, and 8b have been determined by single-crystal X-ray diffraction.

机译：氨基双（二有机基氨基）膦（R_2N）_2PNH_2（R = iPr（a），Cy（b））与Cp_2MCl_2（M = Ti，Zr，Hf），CpTiCl_3和TiCl_4的反应导致形成过渡金属配合物（R_2N）_2PN（H）MCp_2Cl（M = Ti（1b），Zr（2a，b），Hf（3a，b））（R_2N）_2P（H）NTiCpCl_2（8a，b）和（R_2N）_2P（ H）NTiCl_3（10a，b）。详细介绍了金属片段的电子效应对（NH）-phospanylamido和互变异构体（PH）-亚氨基磷烷形式之间所产生的平衡的影响。计算研究清楚地证实了实验结果。 2a，3a和8b的分子结构已通过单晶X射线衍射确定。

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《Organometallics》 |2001年第9期|共6页
作者
Mochael Raab; Andreas Sundermann; Gerold Schick; Armin Loew; Martin Nieger; Wolfgang W.Schoeller; Edgar Niecke;
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中图分类有机化学;有机质材料;
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1. (NH)-Phosphanylamido-and (PH)-Phosphoraneiminato Transition-Metal Complexes: Syntheses, Structures, and Computational Studies [J] . Mochael Raab, Andreas Sundermann, Gerold Schick, Organometallics . 2001,第9期

机译：（NH）-磷酰胺基和（PH）-磷亚胺基过渡金属配合物：合成，结构和计算研究
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(NH)-Phosphanylamido-and (PH)-Phosphoraneiminato Transition-Metal Complexes: Syntheses, Structures, and Computational Studies

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