Mechanistic Pathways for N2O Elimination from trans-R3Sn-O-N=N-O-SnR3 and for Reversible Binding of CO2 to R3Sn-O-SnR3 (R = Ph, Cy)

Davis, Jack V.; Gamage, Mohan M.; Guio, Oswaldo; Captain, Burjor; Temprado, Manuel; Hoff, Carl D.

doi:10.1021/acs.inorgchem.1c01291

Title: Mechanistic Pathways for N₂O Elimination from trans-R₃Sn-O-N=N-O-SnR₃ and for Reversible Binding of CO₂ to R₃Sn-O-SnR₃ (R = Ph, Cy)

Journal Article · Mon Aug 02 00:00:00 EDT 2021 · Inorganic Chemistry

DOI:https://doi.org/10.1021/acs.inorgchem.1c01291· OSTI ID:2000240

Davis, Jack V. ^[1]; Gamage, Mohan M. ^[1]; Guio, Oswaldo ^[1];

^[1];

^[2];

^[1]

University of Miami, Coral Gables, FL (United States)
Universidad de Alcalá, Madrid (Spain)

The rate and mechanism of the elimination of N₂O from trans-R₃Sn-O-N=N-O-SnR₃ (R = Ph (₁^Ph) and R = Cy (₁^Cy)) to form R₃Sn-O-SnR₃ (R = Ph (₂^Ph) and R = Cy (₂^Cy)) have been studied using both NMR and IR techniques to monitor the reactions in the temperature range of 39–79 °C in C₆D₆. Activation parameters for this reaction are ΔH^‡ = 15.8 ± 2.0 kcal·mol^–1 and ΔS^‡ = –28.5 ± 5 cal·mol^–1·K^–1 for ₁^Ph and ΔH^‡ = 22.7 ± 2.5 kcal·mol^–1 and ΔS^‡ = –12.4 ± 6 cal·mol^–1·K^–1 for ₁^Cy. Addition of O₂, CO₂, N₂O, or PPh₃ to sealed tube NMR experiments did not alter in a detectable way the rate or product distribution of the reactions. Computational DFT studies of elimination of hyponitrite from trans-Me₃Sn-O-N=N-O-SnMe₃ (₁^Me) yield a mechanism involving initial migration of the R₃Sn group from O to N passing through a marginally stable intermediate product and subsequent N₂O elimination. Reactions of ₁^Ph with protic acids HX are rapid and lead to formation of R₃SnX and trans-H₂N₂O₂. Reaction of ₁^Ph with the metal radical •Cr(CO)₃C₅Me₅ at low concentrations results in rapid evolution of N₂O. At higher •Cr(CO)₃C₅Me₅ concentrations, evolution of CO₂ rather than N₂O is observed. Addition of 1 atm or less CO₂ to benzene or toluene solutions of ₂^Ph and ₂^Cy resulted in very rapid reaction to form the corresponding carbonates R₃Sn-O-C(=O)-O-SnR₃ (R = Ph (₃^Ph) and R = Cy (₃^Cy)) at room temperature. Evacuation results in fast loss of bound CO₂ and regeneration of ₂^Ph and ₂^Cy. Variable temperature data for formation of ₃^Cy yield ΔH^o = –8.7 ± 0.6 kcal·mol^–1, ΔS^o = –17.1 ± 2.0 cal·mol^–1·K^–1, and ΔG^o_298K = –3.6 ± 1.2 kcal·mol^–1. Furthermore, DFT studies were performed and provide additional insight into the energetics and mechanisms for the reactions.

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Research Organization:: University of Miami, Coral Gables, FL (United States)

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

Grant/Contract Number:: SC0019456

OSTI ID:: 2000240

Journal Information:: Inorganic Chemistry, Vol. 60, Issue 16; ISSN 0020-1669

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

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Title: Mechanistic Pathways for N2O Elimination from trans-R3Sn-O-N=N-O-SnR3 and for Reversible Binding of CO2 to R3Sn-O-SnR3 (R = Ph, Cy)

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Title: Mechanistic Pathways for N₂O Elimination from trans-R₃Sn-O-N=N-O-SnR₃ and for Reversible Binding of CO₂ to R₃Sn-O-SnR₃ (R = Ph, Cy)