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, t Bu, Ph, TMS, Hyp = (Si(SiMe 3 ) 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(SiMe 3 )-K•DME]. In addition to that, a novel monomeric diphosphastannylene [HypP(SiMe 3 )] 2 Sn was isolated as well as confirmed by experimental and calculated NMR data and single crystal X-ray analysis.
The novel diphosphatrisilanes {(R2P‐Si(SiMe3)2‐)2‐SiMe2} [R = Ph, H] and the cyclophosphatrisilabutanes {R–PSi3} [R = H, SiMe3] have been prepared via salt metathesis reactions between phosphanides and 2,4‐dihalogenated pentasilanes and characterized via NMR spectroscopy. The experimental results were supported by DFT calculations. Although P–Si bond formation was observed in all cases, the outcome of the reactions varied depending on the nature of ligands on the phosphanides, forming either linear diphosphatrisilanes or cyclic phosphatrisilacyclobutanes. DFT studies were performed to get a better understanding of the reactions. The precursor silanes were fully characterized using NMR spectroscopy and single‐crystal X‐ray diffraction and offer interesting building blocks. In addition, a modified route for the synthesis of P(TMS)3 was successfully carried out, achieving high yields of up to 73 %, circumventing the use of white phosphorus and phosphine gas during the reaction.
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