Exploration of Novel α,ω‐Substituted Diphosphatrisilanes by Combining Experimental Methods and DFT Calculations

Abstract

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.

Linear Phenylsilanes with PSi4P, PSi5P, and Si7 Backbones

“…They presented the preparation of 1,1,1,3,3,5,5,5octamethyl-2,4-bis(trimethylsilyl)pentasilyl-2,4-diphosphane with À PH 2 and À PPh 2 substituents. [35] Cyclic and polycyclic phosphasilanes were presented in the literature by different working groups around Drieß, [36,37] Fritz, [38][39][40][41][42] Hönle [43,44] and some other researchers, [45][46][47][48][49][50]35] but the substituents were aliphatic groups in most cases. Perarylated phosphasilanes might be more suitable precursors for the preparation of hydridphosphasilanes, as it has been shown for the pure hydridosilanes.…”

“…They presented the preparation of 1,1,1,3,3,5,5,5‐octamethyl‐2,4‐bis(trimethylsilyl)pentasilyl‐2,4‐diphosphane with −PH 2 and −PPh 2 substituents [35] . Cyclic and polycyclic phosphasilanes were presented in the literature by different working groups around Drieß, [36,37] Fritz, [38–42] Hönle [43,44] and some other researchers, [45–50,35] but the substituents were aliphatic groups in most cases. Perarylated phosphasilanes might be more suitable precursors for the preparation of hydridphosphasilanes, as it has been shown for the pure hydridosilanes [33] .…”

Simple conversion of trisodium phosphide, Na3P, into silyl- and cyanophosphides and the structure of a terminal silver phosphide

“…10 With methylchlorosilanes Me 4−x SiCl x (x = 1, 2, 3) as reagents, complex product mixtures are obtained and only with 3.3 equivalents of Me 3 SiCl (TMSCl) a fair yield of P(TMS) 3 (52%) is achieved after distillation, consistent with previous work (Scheme 2(b)). 18 Notably, this reaction proceeds without the addition of phosphonium or ammonium salts.…”