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Synthesis and Theoretical Investigation of Diphosphastannylenes

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posted on 29.08.2018, 18:44 by Elisabeth Schwarz, Stefan K. Mueller, Gernot Weinberger, Ana Torvisco, Michaela Flock
The factors affecting the stabilization of diphosphastannylenes, such as substituent size, steric demand, and type of substituent (aryl, alkyl, silyl) were investigated via a comprehensive DFT and experimental investigation. The influence of various substituents (H, Me, tBu, Ph, TMS, Hyp = (Si­(SiMe3)3)) on the pyramidalization of the phosphorus centers and cone angle determination of those substituents were carried out. Through these considerations, ligand systems capable of isolating a stable Sn­(II) species were determined. Synthetic work led to the isolation of dimeric supermesityl­(trimethylsily)­phosphanides, 2,4,6-tris­(t-butyl)­phenyl trimethylsilyl lithium phosphanide, 2,4,6-tris­(t-butyl)­phenyl trimethylsilyl potassium phosphanide, and one hypersilylphosphanide [HypP­(SiMe3)­K·DME]. In addition to that, a novel monomeric diphosphastannylene [HypP­(SiMe3)]2Sn was isolated as well as confirmed by experimental and calculated NMR data and single crystal X-ray analysis.