Some insertion reactions into the Ti–Me bond of [Ti(η5-C5Me5)MeCl2]; crystal structures of [Ti(η5-C5Me5)(η2-COMe)Cl2] and [{Ti(η5-C5Me5)}2(µ-Cl)2{µ-η4-CH2-(2,6-me2C6H3N)CC(NC6H3Me2-2,6)CH2}]
- 1 January 1993
- journal article
- research article
- Published by Royal Society of Chemistry (RSC) in J. Chem. Soc., Dalton Trans.
- No. 14,p. 2117-2122
- https://doi.org/10.1039/dt9930002117
Abstract
Treatment of [Ti(C5Me5)Cl3] with trimethylaluminium gives [Ti(C5Me5)MeCl2], which reacts readily with CO, CNC6H3Me2-2,6 and N2CPh2 to give the corresponding acyl [Ti(C5Me5)(η2-COMe)Cl2], iminoacyl [Ti(C5Me5){η2-MeCN(C6H3Me2-2,6)}Cl2] and hydrazonato [Ti(C5Me5){η2-N(Me)NCPh2}Cl2] insertion products. The compound [Ti(C5Me5)(η2-COMe)Cl2] reacts with PMe3 to give [Ti(C5Me5){η2-OC(PMe3)Me}Cl2] and [Ti(C5Me5){OC(CNC6H3Me2-2,6)Me}Cl2] has been identified by NMR spectroscopy as the product of a similar nucleophilic attack by CNC6H3Me2-2,6. The reaction of [Ti(C5Me5){η2-MeCN(C6H3Me2-2,6)}Cl2] with nucleophilic agents like Li[N(SiMe3)2] leads to [{Ti(C5Me5)}2(µ-Cl)2{µ-η4-CH2(2,6-Me2C6H3N)CC(NC6H3Me2-2,6)CH2}]. The crystal structures of the latter and of [Ti(C5Me5)(η2-COMe)Cl2] have been established by X-ray diffraction methods; the mononuclear compound shows a pseudo-square-pyramidal geometry with a strong Ti–[η2-C(Me)O] interaction, while the dinuclear compound contains two Ti(C5Me5) groups bridged by two chlorine atoms and by the new ligand η4-CH2(2,6-Me2C6H3N)CC(NC6H3Me2-2,6)CH2 reported here for the first time.Keywords
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