| Autor: |
Zhang, Jie, Hou, Yuanfeng, Liu, Shihua, Lin, Jieli, Li, Zhongshu |
| Předmět: |
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| Zdroj: |
Dalton Transactions: An International Journal of Inorganic Chemistry; 3/28/2024, Vol. 53 Issue 12, p5608-5615, 8p |
| Abstrakt: |
Profound insight into the electronic structures of occasionally observed μ2-P bridging phosphinines remains limited. In this work, we present the isolation and X-ray crystallographic characterization of a dimeric Rh(I) phosphinine complex exhibiting both η1-P and μ2-P phosphinine coordination modes. Variable temperature NMR analyses and DOSY spectrum measurement confirmed the presence of two types of fluxional phenomena in solution: η1-P phosphinine bonding and dissociation, and η1-P and μ2-P equilibrium. DFT calculations in conjunction with single crystal X-ray diffraction studies suggest that the μ2-P phosphinines donate four electrons via a σ-lone pair and a high-lying π-type electron pair, instead of two σ-lone pairs, forming σ- and π-three-center-two-electron bonds. The stronger π-type interactions lead to longer P–C bonds and larger negative coordination chemical shifts for μ2-P phosphinines. However, the binding interactions of μ2-P are thermodynamically weaker than those of η1-P. Reactivity studies further confirm the labile nature of the μ2-P phosphinine bonds, which could be easily converted to an η1-P phosphinine. [ABSTRACT FROM AUTHOR] |
| Databáze: |
Complementary Index |
| Externí odkaz: |
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