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Intermolecular N–H Oxidative Addition of Ammonia, Alkylamines, and Arylamines to a Planar σ3-Phosphorus Compound via an Entropy-Controlled Electrophilic Mechanism

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Department of Chemistry, The Pennsylvania State University, University Park, Pennsylvania 16802, United States
§ Department of Chemical Engineering, The Pennsylvania State University, University Park, Pennsylvania 16802, United States
Department of Chemistry and Biochemistry, Brigham Young University, Provo, Utah 84602, United States
Cite this: J. Am. Chem. Soc. 2014, 136, 12, 4640–4650
Publication Date (Web):March 5, 2014
https://doi.org/10.1021/ja412469e
Copyright © 2014 American Chemical Society

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    Abstract

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    Ammonia, alkyl amines, and aryl amines are found to undergo rapid intermolecular N–H oxidative addition to a planar mononuclear σ3-phosphorus compound (1). The pentacoordinate phosphorane products (1·[H][NHR]) are structurally robust, permitting full characterization by multinuclear NMR spectroscopy and single-crystal X-ray diffraction. Isothermal titration calorimetry was employed to quantify the enthalpy of the N–H oxidative addition of n-propylamine to 1 (nPrNH2 + 11·[H][NHnPr], ΔHrxn298 = −10.6 kcal/mol). The kinetics of n-propylamine N–H oxidative addition were monitored by in situ UV absorption spectroscopy and determination of the rate law showed an unusually large molecularity (ν = k[1][nPrNH2]3). Kinetic experiments conducted over the temperature range of 10–70 °C revealed that the reaction rate decreased with increasing temperature. Activation parameters extracted from an Eyring analysis (ΔH = −0.8 ± 0.4 kcal/mol, ΔS = −72 ± 2 cal/(mol·K)) indicate that the cleavage of strong N–H bonds by 1 is entropy controlled due to a highly ordered, high molecularity transition state. Density functional calculations indicate that a concerted oxidative addition via a classical three-center transition structure is energetically inaccessible. Rather, a stepwise heterolytic pathway is preferred, proceeding by initial amine-assisted N–H heterolysis upon complexation to the electrophilic phosphorus center followed by rate-controlling N → P proton transfer.

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    Additional synthetic procedures including the preparation of 1; 1H, 13C, and 31P spectra; crystallographic details for 1·[H][NHMes]; procedures and data for kinetic studies, computational details including Cartesian coordinates for stationary points. This material is available free of charge via the Internet at http://pubs.acs.org.

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