An Isolable Terminal Imido Complex of Platinum

Abstract Late transition-metal imido species serve as key intermediates in a variety of catalytic transformations. However, their transient nature renders isolation challenging, and an isolable platinum terminal imido complex has remained elusive to date. In this work, we present a platinum terminal imido complex [(tBuXantphos)Pt(κ-N-NTs)] (tBuXantphos = 9,9-dimethyl-4,5-bis(di-tert-butylphosphino)xanthene, Ts = tosyl) that was prepared by the reaction of the platinum(0) complex [(tBuXantphos)Pt] with tosyl azide and fully characterized by NMR spectroscopy, single-crystal X-ray diffraction, and a Pt L3-edge X-ray absorption near-edge structure study. The platinum imido complex features a Pt–N distance of 1.978(6) Å and a bent Pt–N–S angle of 131.0(4) degrees. Computational studies suggest that the Pt–N bond is essentially a polarized σ-bond with weak π-interaction character and is associated with a strong attractive electrostatic interaction. Reactivity studies revealed that the platinum imido complex can perform nitrene transfer reactions with phosphines, CO, and isocyanides, and can also react with electrophiles to generate platinum(II) amido compounds as well as ion-pair species containing an amide anion as the counterion.