Phosphinoyl-Substituted Ketenyl Anions: Synthesis and Substituent Effects on the Structural Properties.

ABSTRACT: Ketenyl anions are versatile intermediates in synthetic chemistry and have recently become accessible as isolable reagents from metalated ylides by exchange of the phosphine with CO. Herein, we report on a systematic study of substituent effects on the structure and bonding situation in ketenyl anions. A series of phosphinoyl-substituted ketenyl anions {[R₂P(X)CCO]^- with X = O, NTol, S, Se} were prepared by carbonylation of the corresponding yldiides and isolated as their corresponding potassium salts. NMR and IR spectroscopic analyses together with computational studies demonstrate that the more electron-withdrawing oxo- and iminophosphinoyl substituents increase the s-character in the bond to the ketene moiety and hence the ynolate character of the anion. This trend is particularly seen in solution, whereas the solid-state properties are influenced by packing effects affecting the bonding situation.

SUBMITTER: Jorges M 

PROVIDER: S-EPMC10900514 | biostudies-literature | 2024 Feb

REPOSITORIES: biostudies-literature