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    Reactivity enhancement of a diphosphene by reversible N-heterocyclic carbene coordination
    (Royal Society of Chemistry, 2018) Dhara, Debabrata; Kalita, Pankaj; Mondal, Subhadip; Narayanan, Ramakirushnan Suriya; Mote, Kaustubh R.; Huch, Volker; Zimmer, Michael; Yıldız, Cem Burak; Scheschkewitz, David; Chandrasekhar, Vadapalli; Jana, Ankul
    Diphosphene TerMesP = PTerMes (1; TerMes = 2,6-Mes2C6H3; Mes = 2,4,6-Me3C6H2) and NHCMe42 (NHCMe4 = 1,3,4,5-tetramethylimidazol-2-ylidene) exist in an equilibrium mixture with the NHCMe4-coordinated diphosphene 3. While uncoordinated 1 is inert to hydrolysis, the NHC adduct 3 readily undergoes hydrolysis to afford a phosphino-substituted phosphine oxide with the liberation of NHCMe4. On this basis, conditions suitable for the catalytic use of NHCMe4 were identified. Similarly, while the hydrogenation of free diphosphene 1 with H3N·BH3 is very slow, 3 reacts instantaneously with H3N·BH3 at room temperature to afford a dihydrodiphosphane. © 2018 The Royal Society of Chemistry.