Mechanistic Pathways for N2O Elimination from trans-R3Sn-O-NâN-O-SnR3 and for Reversible Binding of CO2 to R3Sn-O-SnR3 (R = Ph, Cy).
Inorg Chem
; 60(16): 12075-12084, 2021 Aug 16.
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| ID: mdl-34338521
ABSTRACT
The rate and mechanism of the elimination of N2O from trans-R3Sn-O-NâN-O-SnR3 (R = Ph (1Ph) and R = Cy (1Cy)) to form R3Sn-O-SnR3 (R = Ph (2Ph) and R = Cy (2Cy)) 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 1Ph and ΔH⧧ = 22.7 ± 2.5 kcal·mol-1 and ΔS⧧ = -12.4 ± 6 cal·mol-1·K-1 for 1Cy. 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-NâN-O-SnMe3 (1Me) 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 1Ph with protic acids HX are rapid and lead to formation of R3SnX and trans-H2N2O2. Reaction of 1Ph with the metal radical â¢Cr(CO)3C5Me5 at low concentrations results in rapid evolution of N2O. At higher â¢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 2Ph and 2Cy resulted in very rapid reaction to form the corresponding carbonates R3Sn-O-C(âO)-O-SnR3 (R = Ph (3Ph) and R = Cy (3Cy)) at room temperature. Evacuation results in fast loss of bound CO2 and regeneration of 2Ph and 2Cy. Variable temperature data for formation of 3Cy yield ΔHo = -8.7 ± 0.6 kcal·mol-1, ΔSo = -17.1 ± 2.0 cal·mol-1·K-1, and ΔGo298K = -3.6 ± 1.2 kcal·mol-1. DFT studies were performed and provide additional insight into the energetics and mechanisms for the reactions.
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01-internacional
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MEDLINE
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Revista:
Inorg Chem
Año:
2021
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Article
País de afiliación:
Estados Unidos