Synthesis and Characterization of Substituted Phosphasilenes and its Rare Homologue Stibasilene >Si=Sb

Herein we report the reduction of R‐EX2 (E=P, Sb) with two equivalents of KC8 in the presence of silylene (LSiR; L=PhC(NtBu)2) to give Trip‐P=SiL(C6H4PPh2) (1), TerPh−P=(tBu)SiL (2) and TerPh−Sb=(tBu)SiL (3). The last (3) belongs to a new class of heavier analogues of Schiff bases (>C=N−), contai...

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Published in:Chemistry : a European journal 2023-08, Vol.29 (47), p.e202300791-n/a
Main Authors: Nazish, Mohd, Legendre, Christina M., Herbst‐Irmer, Regine, Muhammed, Shahila, Parameswaran, Pattiyil, Stalke, Dietmar, Roesky, Herbert W.
Format: Article
Language:English
Subjects:
antimony
Chemistry
Imines
phosphasilene
phosphorus
silylene
stibasilene
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Summary:Herein we report the reduction of R‐EX2 (E=P, Sb) with two equivalents of KC8 in the presence of silylene (LSiR; L=PhC(NtBu)2) to give Trip‐P=SiL(C6H4PPh2) (1), TerPh−P=(tBu)SiL (2) and TerPh−Sb=(tBu)SiL (3). The last (3) belongs to a new class of heavier analogues of Schiff bases (>C=N−), containing a formal >Si=Sb− double bond. The theoretical calculations suggest that lone pairs on the dicoordinated group‐15 centers are stabilized by hyperconjugative interactions resulting in pseudo‐Si−P/Si−Sb multiple bonds which are highly reactive as indicated by the high first and second proton affinities. Amidinate stabilized low valent phosphasilenes >Si=P− and a heavier homologue stibasilene >Si=Sb− are reported. Compounds 1, 2, and 3 are heavy analogues of imine or Schiff base. In both phosphorus compounds, Si exhibits double bond character. All compounds were fully characterized by multinuclear NMR spectroscopy, mass spectrometry and 1 and 2 also by single‐crystal X‐ray diffraction analysis.
ISSN:0947-6539
1521-3765
DOI:10.1002/chem.202300791