136492-16-5Relevant academic research and scientific papers
Phosphorus-stabilized titanium carbene complexes: Synthesis, reactivity and DFT studies
Lafage, Mathieu,Heuclin, Hadrien,Le Goff, Xavier-Frdric,Saffon-Merceron, Nathalie,Mzailles, Nicolas
, p. 16995 - 17003 (2014)
The synthesis of two novel titanium carbene complexes from the bis(thiophosphinoyl)methanediide geminal dianion 1 (SCS-2) 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.
Sterically Hindered Diphosphines (Ph2P)2C=CHR (R = Me or Ph) and their Derivatives
Bookham, Jonathan L.,Conti, Fosca,McFarlane, H. Christina E.,McFarlane, William,Thornton-Pett, Mark
, p. 1791 - 1798 (2007/10/02)
Reactions of (Ph2P)2C=CHR (R = Me or Ph) with E (E = S or Se) yielded the corresponding mono- and di-chalcogenides and the mixed S/Se derivatives, 1H, 13C and 31P NMR parameters for which are reported.These are rationalized in terms of conformational preferences associated with the relative P-E and phosphorus-Ione pair orientations.The complexes > (M = Mo or W, R = Me or Ph) have also been prepared and have NMR parameters which can be accounted for similarly.The crystal structure of (Ph2P)2C=CHMe has been determined by single-crystal X-ray diffraction and shows that the solid-state conformation is similar to that deduced in solution on the foregoing basis.
Reactivity of carbanions stabilized by two alpha phosphorus groups
Goli,Grim
, p. 3631 - 3634 (2007/10/02)
The stabilized anion {[Ph2P(S)]2CH}- with lithium as counter cation 1a reacts with formaldehyde or benzaldehyde to give vinylidene phosphine sulfides [Ph2P(S)]2C=CHR, where R is H or Ph, respectively
