Abstract
The reaction of the arylchlorosilylene-NHC adduct ArSi(NHC)Cl [Ar = 2,6-Trip(2)-C6H3; NHC = (MeC)(2-)(NMe)(2)C] 1 with one molar equiv of LiPH2. dme (dme = 1,2dimethoxyethane) 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)=PSiMe3 5 could be synthesized and structurally characterized. DFT studies confirmed that the Si=P bond in 2 and 4 is mostly zwitterionic with drastically decreased double-bond character.
Original language | English |
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Pages (from-to) | 15060-15063 |
Number of pages | 4 |
Journal | Angewandte Chemie-International Edition |
Volume | 54 |
Issue number | 50 |
DOIs | |
Publication status | Published - 7 Dec 2015 |
Keywords
- heavier olefin analogues
- multiple bonds
- phosphorus
- silicon
- zwitterions
- HALF-PARENT PHOSPHASILENE
- X-RAY-STRUCTURE
- SILICON-PHOSPHORUS
- ZWITTERIONIC PHOSPHASILENE
- UNUSUAL REACTIVITY
- DOUBLE-BONDS
- SI-P
- COMPLEXES
- PHOSPHANES
- CHEMISTRY