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- Title
Phosphorus-Stabilized Titanium Carbene Complexes: Synthesis, Reactivity and DFT Studies.
- Authors
Lafage, Mathieu; Heuclin, Hadrien; Le Goff, Xavier ‐ Frédéric; Saffon ‐ Merceron, Nathalie; Mézailles, Nicolas
- Abstract
The synthesis of two novel titanium carbene complexes from the bis(thiophosphinoyl)methanediide geminal dianion 1 (SCS2-) is described. Dianion 1 reacts cleanly with 0.5 equivalents of [TiCl4(thf)2] to afford the bis-carbene complex [(SCS)2Ti] (2) in 86% yield. The mono-carbene complex [(SCS)TiCl2(thf)] (3) can also be obtained by using an excess of [TiCl4(thf)2]. The structures of 2 and 3 are confirmed by Xray crystallography. A strong nucleophilic reactivity towards various electrophiles (ketones and aldehydes) is observed. The reaction of 3 with N,N'-dicyclohexylcarbodiimide (DCC) and phenyl isocyanate leads to the formation of two novel diphosphinoketenimines 8a and 8b. The bis-titanium guanidinate complex 9 is trapped as the by-product of the reaction with DCC. The X-ray crystal structures of 8a and 9 are presented. The mechanism of the reaction between complex 3 and DCC is rationalized by DFT studies.
- Subjects
TITANIUM compounds synthesis; CARBENE analogues; REACTIVITY (Chemistry); NUCLEOPHILIC reactions; REACTION mechanisms (Chemistry); DENSITY functional theory; CRYSTAL structure
- Publication
Chemistry - A European Journal, 2014, Vol 20, Issue 51, p16995
- ISSN
0947-6539
- Publication type
Article
- DOI
10.1002/chem.201403708