221657-80-3Relevant academic research and scientific papers
Reactions of TiCl4 with phosphines and alkylating reagents: An organometallic route to a titanium(II) cluster compound1
Cotton, F. Albert,Murillo, Carlos A.,Petrukhina, Marina A.
, p. 78 - 86 (1999)
Treatment of TiCl4 with a stoichiometric amount of 1,2-bis(dimethylphosphino)ethane (dmpe) gives TiCl4(dmpe) (1). This compound can be readily alkylated by 1 or 2 equivalents of PhCH2MgCl affording TiCl3(PhCH2)(dmpe) (2) and TiCl2(PhCH2)2(dmpe) (3), respectively. Syntheses and crystal structures of the three mononuclear titanium(IV) compounds 1-3 are presented. Decomposition of 'TiCl3(But)(dmpe)' produces the dinuclear titanium(III) edge-sharing complex, Ti2Cl4(μ-Cl)2(dmpe)2 (4a). Its analogue, Ti2Cl4(μ-Cl)2(depe)2 (4b) has been obtained by direct reaction of TiCl3(THF)3 with the corresponding phosphine. Thermal decomposition of 'TiCl2(But)2(dmpe)' provides the first true, molecular metal atom cluster of titanium(II), Ti3Cl6(dmpe)3 (5). The cluster molecule consists of an equilateral triangle of TiII atoms with three coplanar μ-Cl atoms bridging the edges. Each titanium atom is further coordinated by a chelating dmpe molecule and a chloride ion, with Ti-Ti distances of 2.872(3) A. The compound appears to be slightly paramagnetic but this is probably the result of a small amount of decomposition due to the difficulty of handling this pyrophoric complex. It is proposed that there are genuine Ti-Ti single bonds, and that this is a true metal atom cluster compound.
