A Persistent 1,2‐Dihydrophosphasilene Adduct | Zendy

Hansen Kerstin | Zendy; Szilvási Tibor | Zendy; Blom Burgert | Zendy; Driess Matthias | Zendy

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A Persistent 1,2‐Dihydrophosphasilene Adduct

Author(s) -

Hansen Kerstin,

Szilvási Tibor,

Blom Burgert,

Driess Matthias

Publication year - 2015

Publication title -

angewandte chemie international edition

Language(s) - English

Resource type - Journals

SCImago Journal Rank - 5.831

H-Index - 550

eISSN - 1521-3773

pISSN - 1433-7851

DOI - 10.1002/anie.201508149

Subject(s) - adduct , chemistry , molar ratio , silylation , medicinal chemistry , stereochemistry , catalysis , organic chemistry

The reaction of the arylchlorosilylene–NHC adduct ArSi(NHC)Cl [Ar=2,6‐Trip 2 ‐C 6 H 3 ; NHC=(MeC) 2 (NMe) 2 C] 1 with one molar equiv of LiPH 2 . dme (dme=1,2‐dimethoxyethane) affords the first 1,2‐dihydrophosphasilene adduct 2 (ArSi(NHC)(H)PH). The latter is labile in solution and can undergo head‐to‐tail dimerization to give [ArSi(H)PH] 2 3 and “free” NHC. Further stabilization of 2 by complexation with {W(CO) 5 } affords the isolable 1,2‐dihydrophosphasilene–tungsten complex 4 [ArSi(NHC)(H)P(H)W(CO) 5 ]. Additionally, the new 1‐silyl‐2‐hydrophosphasilene ArSi(NHC)(H)PSiMe 3 5 could be synthesized and structurally characterized. DFT studies confirmed that the SiP bond in 2 and 4 is mostly zwitterionic with drastically decreased double‐bond character.

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