ISSN:
1434-1948
Keywords:
Alkyne complexes
;
Titanium
;
Zirconium
;
Coordination mode
;
Metallacycles
;
Cyclopentadienes
;
Chemistry
;
General Chemistry
Source:
Wiley InterScience Backfile Collection 1832-2000
Topics:
Chemistry and Pharmacology
Notes:
The influence of metals, alkyne substituents, Cp substitution and additional ligands on the stability of bridged and unbridged η2-alkyne-titanocene and -zirconocene complexes has been investigated. The reduction of the complex [(η5-C5H4)-SiMe2-(η5-C5H4)]TiCl2 with magnesium in the presence of tolan (PhC2Ph) does not give the expected alkyne-titanocene complex [(η5-C5H4)-SiMe2-(η5-C5H4)]Ti(η2-PhC2Ph) but by coupling of two tolan molecules the corresponding titanacyclopentadiene [(η5-C5H4)-SiMe2-(η5-C5H4)]TiC4Ph4 (1) was obtained. In the analogous reaction with Me3SiC2SiMe3 the stable η2-alkyne complex without additional ligands [(η5-C5H4)-SiMe2-(η5-C5H4)]Ti(η2-Me3SiC2SiMe3) (2) was formed, due to the sterical influence of the alkyne substituents. The compounds without additional ligands (thi)2Ti(η2-PhC2Ph) (3) and (thi)2Ti(η2- Me3SiC2SiMe3) (5) were isolated from the unbridged titanocene complex (thi)2TiCl2 (thi = tetrahydroindenyl). Two equivalents of complex 3 reacted with one equivalent of water to yield the dimeric alkylidene-μ-oxo complex [(thi)2Ti(CPh=CHPh)]2(μ-O) (6). The reaction of the unbridged zirconocene compound (thi)2ZrCl2 gave the alkyne complex (thi)2Zr(THF)(η2-Me3- SiC2SiMe3) (7) which is stabilized by THF. At higher temperature THF was eliminated from the orange complex 7 forming the green complex (thi)2Zr(η2-Me3SiC2SiMe3). This behaviour was investigated in detail using NMR spectroscopy and compared to similar complexes such as Cp2Zr(η2-Me3SiC2SiMe3) (not stable without THF), (ebthi)2Zr(η2-Me3SiC2SiMe3) (ebthi = ethylenebistetrahydroindenyl; stable without THF) and Cp*2Zr(η2-Me3SiC2SiMe3) (Cp* = pentamethyl-Cp, stable without THF). All complexes were characterized by spectroscopic methods. X-ray structural determinations were conducted for the complexes 1, 3 and 7. Compound 3 is the first example of a structurally characterized tolan-titanocene complex without additional ligands.
Type of Medium:
Electronic Resource
