Phosphorus‐Stabilized Titanium Carbene Complexes: Synthesis,Reactivity and DFT Studies

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 X‐ray 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 8 a and 8 b . The bis‐titanium guanidinate complex 9 is trapped as the by‐product of the reaction with DCC. The X‐ray crystal structures of 8 a and 9 are presented. The mechanism of the reaction between complex 3 and DCC is rationalized by DFT studies.     

Mixed (PS/PO)‐Stabilized Geminal Dianion: Facile Diastereoselective Intramolecular C?H Activations by a Related Ruthenium–Carbene Complex

A new unsymmetrical geminal dianion that contained both a phosphine oxide moiety and a phosphine sulfide moiety has been synthesized. Its reactivity towards Ru^II was explored, which led to the formation of a highly reactive carbene complex that evolved at room temperature to yield a kinetic orthometalated Ru^II complex through C? H activation of the phenyl group of the phosphine oxide moiety. This insertion was found to be thermally reversible and a second C? H insertion occurred at a phenyl group of the phosphine sulfide moiety to form the thermodynamic orthometalated Ru^II complex in a diastereospecific manner. DFT calculations fully rationalized the experimental findings in terms of the relative energies of the kinetic and thermodynamic products and allowed the mechanism of this process to be fully understood.     

Local search and constraint programming for the post enrolment-based course timetabling problem

We present a variety of approaches for solving the post enrolment-based course timetabling problem, which was proposed as Track 2 of the 2007 International Timetabling Competition. We approach the problem using local search and constraint programming techniques. We show how to take advantage of a list-colouring relaxation of the problem. Our local search approach won Track 2 of the 2007 competition. Our best constraint programming approach uses an original problem decomposition. Incorporating this into a large neighbourhood search scheme seems promising, and provides motivation for studying complete approaches in further detail.