N‐Heterocyclic Phosphido Complexes of Rhodium Supported by a Rigid Pincer Ligand,European Journal of Inorganic Chemistry

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N‐Heterocyclic Phosphido Complexes of Rhodium Supported by a Rigid Pincer Ligand
European Journal of Inorganic Chemistry ( IF 2.2 ) Pub Date : 2020-07-01 , DOI: 10.1002/ejic.202000390
Gregory P. Hatzis ₁ , Leah K. Oliemuller ₁ , Diane A. Dickie ₂ , Christine M. Thomas ₁

Affiliation

The diphosphine, N‐heterocyclic phosphenium/phosphido (NHP⁺)/(NHP^–)‐containing ligand (PPP^+/–) has been coordinated to rhodium to study the coordination chemistry of group 9 metals and NHP^+/– fragments. Addition of the chlorophosphine ligand PP^ClP to [Rh(COD)Cl]₂ produces the complex (PP^ClP)RhCl (2 ), which can be reduced to form (PPP)Rh(PMePh₂) (3 ), the asymmetric dimer [(PPP)Rh]₂ (4 ), and the asymmetric dimer [(PPP)Rh(CN^tBu)]₂ (5 ). Analysis of the solid‐state structures and computational studies have provided insight into the electronic structure and bonding in 3–5 , revealing that the NHP^+/– fragments in 3, 4 , and 5 are best described using an NHP^–/Rh^I description. Both 3 and 5 were found to be reactive towards the S–H bond of thiophenol, generating (PPP)RhSPh (6 ) and (PPP)Rh(SPh)(CN^tBu) (7 ), respectively.

中文翻译：

刚性钳配体支持的铑的N-杂环磷杂合物

二膦，N-杂环phosphenium /膦（NHP ⁺）/（NHP ^-）基配体（PPP ^+/-）已被协调，以铑研究组9的金属和NHP的配位化学^+/-片段。在[Rh（COD）Cl] _2中添加氯膦配体PP ^Cl P可生成（PP ^Cl P）RhCl（2）络合物，可将其还原为不对称的（PPP）Rh（PMePh ₂）（3）。二聚体[（PPP）Rh] ₂（4）和不对称二聚体[（PPP）Rh（CN ^t Bu）] ₂（5）。对固态结构的分析和计算研究提供了对3–5中电子结构和键合的深入了解，揭示了使用NHP ^– / Rh ^I描述可以最好地描述3、4和5中的NHP ^+/–片段。。两个3和5中发现，产生（PPP）RhSPh（是朝着苯硫酚的S-H键反应6（CN）和（PPP）的Rh（SPH）^吨卜）（7分别地）。

更新日期：2020-08-10

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