Substituent Effect at Bridgehead Silicon Atom of SMAPs Bicyclic Trialkylphosphines

摘要

A series of silicon-constrained monodentate trialkylphosphones SMAPs bearing Si-substituents of various electronic effects were synthesized via hydrosilane derivative H-SMAP sulfide.Both DFT calculations (values of molecular electrostatic potential minimum) and kinetics studies on P-alkylation indicated that the electronic characters of the phosphine lone pair are substantially influenced by the distal Si-substituents.