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New Route to Access an Acyl‐Functionalized Phosphasilene and a Four‐Membered Si‐P‐C‐O Heterocycle
Author(s) -
Breit Nora C.,
Szilvási Tibor,
Inoue Shigeyoshi
Publication year - 2014
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.201402693
Subject(s) - double bond , chemistry , cycloaddition , silicon , phosphorus , carbon fibers , medicinal chemistry , stereochemistry , nuclear magnetic resonance spectroscopy , polymer chemistry , organic chemistry , materials science , catalysis , composite number , composite material
An acyl‐functionalized phosphasilene, LSi(CO t Bu)P(SiMe 3 ) (L=PhC(N t Bu) 2 ) was synthesized on a new route by the addition of t BuCOCl to the phosphinosilylene LSiP(SiMe 3 ) 2 and subsequent Me 3 SiCl elimination. DFT studies elucidated its molecular structure, the influence of the acyl group on UV/Vis transitions, and revealed the mechanism. The intermediate LSi(CO t Bu)ClP(SiMe 3 ) 2 , with a five‐coordinate silicon center, was characterized by NMR spectroscopy and X‐ray analysis. On the other hand, phosphasilene LSi(SiMe 3 )P(SiMe 3 ) reacted with t BuCOCl by a [2+2] cycloaddition of the silicon–phosphorus double bond and the carbon–oxygen double bond in addition to Me 3 SiCl elimination, thereby affording the novel, fully characterized compound LSi(SiMe 3 )[PC( t Bu)O] bearing a Si‐P‐C‐O heterocycle with a phosphorus–carbon double bond. DFT studies suggest that two mechanisms occur simultaneously.