A Persistent 1,2-Dihydrophosphasilene Adduct.
The reaction of the arylchlorosilylene-NHC adduct ArSi(NHC)Cl [Ar=2,6-Trip2 -C6 H3 ; NHC=(MeC)2 (NMe)2 C] 1 with one molar equiv of LiPH2 (.) 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)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.
Department of Chemistry: Metalorganics and Inorganic Materials, Technische Universität Berlin, Strasse des 17. Juni 135, Sekr. C2, 10623 Berlin (Germany).
Kerstin
K
Hansen
Department of Inorganic and Analytical Chemistry, Budapest University of Technology and Economics, Szent Gellért tér 4, 1111 Budapest (Hungary).
Tibor
T
Szilvási
Department of Chemistry: Metalorganics and Inorganic Materials, Technische Universität Berlin, Strasse des 17. Juni 135, Sekr. C2, 10623 Berlin (Germany).|Current address: Faculty of Humanities and Sciences, Maastricht University, Lenculenstraat 14, 6211 KR Maastricht (The Netherlands).
Burgert
B
Blom
Department of Chemistry: Metalorganics and Inorganic Materials, Technische Universität Berlin, Strasse des 17. Juni 135, Sekr. C2, 10623 Berlin (Germany). matthias.driess@tu-berlin.de.
Matthias
M
Driess
heavier olefin analogues; multiple bonds; phosphorus; silicon; zwitterions