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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 · · Inorganic Chemistry
 [1];  [2];  [2];  [2];  [3];  [2]
  1. University of Miami, Coral Gables, FL (United States); University of Miami
  2. University of Miami, Coral Gables, FL (United States)
  3. Universidad de Alcalá, Madrid (Spain)
+ Show Author Affiliations
The rate and mechanism of the elimination of N2O from trans-R3Sn-O-N=N-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-N=N-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 •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 2Ph and 2Cy resulted in very rapid reaction to form the corresponding carbonates R3Sn-O-C(=O)-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. Furthermore, DFT studies were performed and provide additional insight into the energetics and mechanisms for the reactions.
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
Alternate ID(s):
OSTI ID: 1853309
Journal Information:
Inorganic Chemistry, Journal Name: Inorganic Chemistry Journal Issue: 16 Vol. 60; ISSN 0020-1669
Publisher:
American Chemical Society (ACS)Copyright Statement
Country of Publication:
United States
Language:
English

References (34)

cis-Sodium Hyponitrite—A New Preparative Route and a Crystal Structure Analysis journal August 1996
Covalent Capture of Nitrous Oxide by N-Heterocyclic Carbenes journal November 2011
Side‐on Coordination in Isostructural Nitrous Oxide and Carbon Dioxide Complexes of Nickel journal February 2021
Effect of the damping function in dispersion corrected density functional theory journal March 2011
Bis(triphenylzinn-und-blei)hyponitrit [(C6H5)3M]2N2O2 (M = Sn, Pb) journal March 1968
Zur Kenntnis von cis-Natriumhyponitrit journal November 1997
Crystal and Molecular Structure of the trans-Hyponitrite Compound Ph3Sn(μ-ONNO)SnPh3 journal February 2011
Synthesis, structure, and thermochemistry of adduct formation between N-heterocyclic carbenes and isocyanates or mesitylnitrile oxide journal July 2013
Imidazolylidenes, imidazolinylidenes and imidazolidines journal December 1999
New triorganotin(IV) complexes of polyfunctional S,N,O-ligands: Supramolecular structures based on π⋯π and/or C–H⋯π interactions journal April 2006
Understanding the Role of Hyponitrite in Nitric Oxide Reduction journal April 2015
Thermodynamic, Kinetic, Structural, and Computational Studies of the Ph 3 Sn–H, Ph 3 Sn–SnPh 3 , and Ph 3 Sn–Cr(CO) 3 C 5 Me 5 Bond Dissociation Enthalpies journal October 2016
Mechanism of N–N Bond Formation by Transition Metal–Nitrosyl Complexes: Modeling Flavodiiron Nitric Oxide Reductases journal March 2018
Examination of the Mechanism of the Yield of N 2 O from Nitroxyl (HNO) in the Solution Phase by Theoretical Calculations journal June 2017
Reduction in Formation Temperature of Ta-Doped Lithium Lanthanum Zirconate by Application of Lux–Flood Basic Molten Salt Synthesis journal June 2020
Production of cis -Na 2 N 2 O 2 and NaNO 3 by Ball Milling Na 2 O and N 2 O in Alkali Metal Halide Salts journal July 2021
Carbon Dioxide Capture in Metal–Organic Frameworks journal September 2011
Characterization of the Bridged Hyponitrite Complex {[Fe(OEP)] 2 (μ-N 2 O 2 )}: Reactivity of Hyponitrite Complexes and Biological Relevance journal June 2014
Kinetic and Thermodynamic Studies of Reaction of •Cr(CO) 3 C 5 Me 5 , HCr(CO) 3 C 5 Me 5 , and PhSCr(CO) 3 C 5 Me 5 with •NO. Reductive Elimination of Thermodynamically Unstable Molecules HNO and RSNO Driven by Formation of the Strong Cr−NO Bond journal December 1999
Potential Energy Surface of the HNO + NO Reaction. An ab Initio Molecular Orbital Study journal February 1995
Laser photolysis study of the reactions of alkoxyl radicals generated in the photosensitized decomposition of organic hyponitrites journal September 1982
The Decomposition of Hyponitrous Acid. I. The Non-chain Reaction journal March 1963
The Decomposition of Hyponitrous Acid. II. The Chain Reaction journal June 1965
Hyponitrite Radical, a Stable Adduct of Nitric Oxide and Nitroxyl journal December 2003
Decomposition rates, synthesis, and spectral properties of a series of alkyl hyponitrites journal October 1983
DFT Study on Activation of Carbon Dioxide by Dimethytin Dimethoxide for Synthesis of Dimethyl Carbonate journal March 2010
Synthetic chemistry with nitrous oxide journal January 2015
Reversible carboxylation of N-heterocyclic carbenesElectronic supplementary information (ESI) available: crystal structure data and ORTEP for 1,3-bis(2,6-diisopropylphenyl)imidazolylium-2-carboxylate (3). See http://www.rsc.org/suppdata/cc/b3/b311350g/ journal January 2004
Balanced basis sets of split valence, triple zeta valence and quadruple zeta valence quality for H to Rn: Design and assessment of accuracy journal January 2005
231. Kinetics and mechanism of the decomposition of hyponitrous acid journal January 1963
Density‐functional thermochemistry. III. The role of exact exchange journal April 1993
Development of the Colle-Salvetti correlation-energy formula into a functional of the electron density journal January 1988
A Bridge-type Sn···O Coordination of Bis(trialkyltin) Carbonates journal February 1967
CO2 Derivatives of Molecular Tin Compounds. Part 1: Hemicarbonato and Carbonato Complexes journal April 2020

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Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
Addition reactions
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Oxides