Thermally-Activated Tunneling in the Two-Water Bridge Catalyzed Tautomerization of Phosphinylidene Compounds.

ABSTRACT: Phosphinylidenes are an important class of organophosphorus compounds that can exhibit tautomerization between tricoordinated P(III) hydroxide (R¹ R² POH) and a pentacoordinated P(V) oxide (R¹ R² P(O)H) form. Herein we show, using the canonical variational transition state theory combined with multidimensional small-curvature tunneling approximation, the dominance of proton tunneling in the two-water-bridged tautomerizations of phosphinous acid and model phosphinylidenes comprising phosphosphinates, H-phosphonates, H-phosphinates and secondary phosphine oxides. Based on the studied system, the contribution of thermally-activated tunneling is predicted to speed up the semiclassical reaction rate by ca. threefold to as large as two orders of magnit

SUBMITTER: Nandi A 

PROVIDER: S-EPMC9804263 | biostudies-literature | 2022 Nov

REPOSITORIES: biostudies-literature