Computational Study of the Proton-Transfer Chemistry of the Silaacetylide Anion

Abstract

Reactions involving two [H,C,Si]- anions with the protonated neutral analogues (HSiCH, H2CSi, and H2SiC) have been studied. Calculations through fourth-order perturbation theory (MP4) suggest possible routes for single-proton transfer between the silaacetylide [HCSi]- anion and neutral species. Various important reaction paths for proton-transfer reactions and internal rearrangements of ion−molecule complexes are discussed. Accurate estimates of the acidity of HSiCH and H2SiC are presented and discussed in light of earlier experimental studies.

Organometallic Chemistry in the Flowing Afterglow: A Review

“…Another computational study of [H,C,Si] -species in which proton-transfer reactions have been examined has been reported. 149 F. Miscellaneous Silicon Negative Anion Studies. One of the earliest FA silicon studies involved nucleophilic additions to cyclic silanes, in which it was shown that (1) F -addition to dimethylsilacyclobutane (DMSCB) yielded both a siliconate and a ring-opened product (eq 28), (2) F -addition to dimethylsilacyclohexane yielded only a siliconate, and (3) (CH 3 ) 4 SiF -softtransferred F -to DMSCB to form the siliconate shown in eq 28a.…”

“…This result is consistent with the experimental work, in which no reaction is observed. Another computational study of [H,C,Si] - species in which proton-transfer reactions have been examined has been reported …”