A Masked Phosphinidene Trapped in a Fluxional NCN Pincer

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• 作者：Dr. Jakub Hyvl ; M. Sc. Wesley Y. Yoshida ; Prof. Dr. Arnold L. Rheingold ; Prof. Dr. Russell P. Hughes and Prof. Dr. Matthew F. Cain
• 刊名：Chemistry - A European Journal
• 出版年：2016
• 出版时间：December 5, 2016
• 年：2016
• 卷：22
• 期：49
• 页码：17562-17565
• 全文大小：1321K
• ISSN：1521-3765

文摘

The trapping of a phosphinidene (R-P) in an NCN pincer is presented. Stabilized phosphinidene 1 was characterized by ³¹P{¹H}, ¹H, and ¹³C{¹H} NMR spectroscopy, exhibiting an averaged C_2v symmetry in solution between −60 and 60 °C. In the solid state, the phosphinidene is coordinated by one adjacent N atom featuring a formal P−N bond (1.757(2) Å) to give a five-membered ring with some aromatic character, confirmed by DFT calculations (B3LYP-D3/6-311G**++) to be the ground-state structure. Equilibration of the two N ligands occurs rapidly in solution via a “bell-clapper”-type process through an associative symmetric transition state calculated to lie 4.0 kcal mol⁻¹ above the ground state.