INFRARED AND SOLID-STATE NMR-STUDIES OF THE ADSORPTION OF PME(2)CL ONSILICA

Dimethylchlorophosphine, PMe(2)Cl reacts with the hydroxyl groups on s ilica at room temperature to yield the chemisorbed speciwes SiOP=O(Me( 2)), gaseous HCl, and gaseous dimethylphosphine, PMe(2)H. rue reaction does not yield SiOPMe(2) in detectable amounts. A mechanism of the re action has been deduced, involving chlorination of the silica, and the generation of Me(2)P=O(H) as an intermediate species; this subsequent ly reacts with PMe(2)Cl to produce a second intermediate Me(2)P=O(Cl). The overall reaction is 2SiOH + 2PMe(2)Cl --> SiCl + HCl + Me(2)PH SiOP=O(Me(2)).