Carbene Supported Dimer of Heavier Ketenimine Analogue with P and Si Atoms.
Abstract: A cyclic alkyl(amino) carbene (cAAC) stabilized dimer [(cAAC)Si(P-Tip)]2 (2) (Tip = 2,4,6-triisopropylphenyl) is reported. 2 can be considered as a dimer of the heavier ketenimine (R2C=C=N-R) analogue. The dark-red rod-shaped crystals of 2 were synthesized by reduction of the precursor, cAAC-dichlorosilylene- stabilized phosphinidene (cAAC)SiCl2 → P-Tip with sodium napthalenide. The crystals of 2 are storable at room temperature for several months, and stable up to 215 °C under an inert atmosphere. X-ray single-crystal diffraction revealed that 2 contains a cyclic non-planar four-membered SiPSiP ring. Magnetic susceptibility measurements confirmed the singlet spin ground state of 2. Cyclic voltammetry of 2 showed a quasi-reversible one-electron reduction indicating the/b formation of the corresponding radical anion 2.-, which was further characterized by EPR measurements in solution. The electronic structure and bonding of 2 and 2·- were studied by theoretical calculations. The experimentally obtained data are in good agreement with the calculated values.