CO Displacement in an Oxidative Addition of Primary Silanes to Rhodium(I)

Biswas, Abhranil; Ellern, Arkady; Sadow, Aaron D.

doi:10.1021/acs.inorgchem.8b03425

CO Displacement in an Oxidative Addition of Primary Silanes to Rhodium(I)

Journal Article · Fri Mar 01 00:00:00 EST 2019 · Inorganic Chemistry

DOI:https://doi.org/10.1021/acs.inorgchem.8b03425· OSTI ID:1502873

Biswas, Abhranil ^[1]; Ellern, Arkady ^[2]; ^[1]

Iowa State Univ., Ames, IA (United States); Ames Lab., Ames, IA (United States)
Ames Lab. and Iowa State Univ., Ames, IA (United States)

The rhodium dicarbonyl {PhB(Ox^Me2)₂Im^Mes}Rh(CO)₂ (1) and primary silanes react by oxidative addition of a nonpolar Si–H bond and, uniquely, a thermal dissociation of CO. These reactions are reversible, and kinetic measurements model the approach to equilibrium. Thus, 1 and RSiH₃ react by oxidative addition at room temperature in the dark, even in CO-saturated solutions. The oxidative addition reaction is first-order in both 1 and RSiH₃, with rate constants for oxidative addition of PhSiH₃ and PhSiD₃ revealing k_H/k_D ~ 1. The reverse reaction, reductive elimination of Si–H from {PhB(Ox^Me₂)₂Im^Mes}RhH(SiH₂R)CO (2), is also first-order in [2] and depends on [CO]. The equilibrium concentrations, determined over a 30 °C temperature range, provide ΔH° = –5.5 ± 0.2 kcal/mol and ΔS° = –16 ± 1 cal·mol^–1K^–1 (for 1 ⇌ 2). The rate laws and activation parameters for oxidative addition (ΔH^‡ = 11 ± 1 kcal·mol^–1 and ΔS^‡ = –26 ± 3 cal·mol^–1·K^–1) and reductive elimination (ΔH^‡ = 17 ± 1 kcal·mol^–1 and ΔS^‡ = –10 ± 3 cal·mol^–1K^–1), particularly the negative activation entropy for both forward and reverse reactions, suggest the transition state of the rate-determining step contains {PhB(Ox^Me₂)₂Im^Mes}Rh(CO)₂ and RSiH₃. Comparison of a series of primary silanes reveals that oxidative addition of arylsilanes is ca. 5× faster than alkylsilanes, whereas reductive elimination of Rh–Si/Rh–H from alkylsilyl and arylsilyl rhodium(III) occurs with similar rate constants. Furthermore, the equilibrium constant K_e for oxidative addition of arylsilanes is >1, whereas reductive elimination is favored for alkylsilanes.

View Accepted Manuscript (DOE)

Research Organization:: Ames Laboratory (AMES), Ames, IA (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)

Grant/Contract Number:: AC02-07CH11358

OSTI ID:: 1502873

Report Number(s):: IS-J--9829

Journal Information:: Inorganic Chemistry, Journal Name: Inorganic Chemistry Journal Issue: 6 Vol. 58; ISSN 0020-1669

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

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