0000000000384853
AUTHOR
Gerardo Jiménez
Synthesis and structural characterization of novel tetranuclear organotitanoxane derivatives.
Synthesis of the novel titanoxane compounds, [(TiCl)(TiOH){(Ti)[μ-(η(5)-C(5)Me(4)SiMe(2)O-κO)](2)(μ-O)}(2)(μ-O)] (4) and [{Ti[μ-(η(5)-C(5)Me(4)SiMe(2)O-κO)](μ-O)}(4)] (5) by controlled reaction of the dinuclear titanium oxo complex [{Ti{μ-(η(5)-C(5)Me(4)SiMe(2)O-κO)}Cl](2)(μ-O)] (1) with 2 equiv of LiOH is reported. Complex 4 is innovative and remarkable. It is one of the rare known examples of tetranuclear stable terminal hydroxo titanium complexes, with an open-chained structure, which coincides with the transient metal monohydroxo proposed in the stepwise pathway employed to justify the formation of the hexanuclear complex [{Ti[μ-(η(5)-C(5)Me(4)SiMe(2)O-κO)](μ-O)}(6)] (3) from 1. (1)H DO…
Stable Methylene- and Oxo-Bridged Monocyclopentadienyl Titanium Compounds. Molecular Structure of {Ti[μ-(η5-C5Me4SiMe2-O)]Me}2(μ-CH2)
Thermolysis of {Ti[μ-(η5-C5Me4SiMe2-O)]Me2}2 affords the methylene-bridged titanium compound {Ti[μ-(η5-C5Me4SiMe2-O)]Me}2(μ-CH2), concurrent with the evolution of methane, the first example of a fu...
Cationic Cyclopentadienyl Phenylenediamido Titanium Species Generated by Reaction of TiCpR[1,2-C6H4(NCH2t-Bu)2]R (CpR = η5-C5H5, η5-C5Me5; R = CH3, CH2Ph) with B(C6F5)3. X-ray Molecular Structure of Ti(η5-C5Me5)[1,2-C6H4(NCH2t-Bu)2][μ-MeB(C6F5)3]
The reaction of TiCpR[1,2-C6H4(NNp)2]R with the Lewis acid B(C6F5)3 in noncoordinating solvent affords the new zwitterionic species TiCpR[1,2-C6H4(NNp)2)][μ-RB(C6F5)3]. When the reaction is performed in dichloromethane, the [μ-RB(C6F5)3]- anion is displaced by solvent molecules, giving ionic products in which the anion is not coordinated. The cyclopentadienyl zwitterionic complexes TiCp[1,2-C6H4(NNp)2)[μ-RB(C6F5)3] decompose via ligand scrambling between boron and titanium to give the neutral titanium complex TiCp[1,2-C6H4(NNp)2](C6F5) along with the byproduct RB(C6F5)2. In contrast, the pentamethylcyclopentadienyl analogues TiCp*[1,2-C6H4(NNp)2][μ-RB(C6F5)3] evolve through C−H activation t…