Fulvalene cyclopentadienyl titanium and zirconium(III) and -(IV) complexes. X-Ray crystal structure of [{Ti(η 5-C 5H 5) Cl} 2 (μ-O)(μ-η 5-η 5-C 10H 8)

Abstract

The reaction of the fulvalene titanium(III) hydride [{Ti(η 5-C 5H 5)(μ-H)}2(μ-η 5-η 5-C 10H 8)] ( 1) with chlorine leads to [{Ti(η 5-C 5H 5)(μ-Cl)} 2(μ-η 5-η 5-C 10H 8)] ( 3) and [{Ti(η 5-C 5H 5)Cl 2} 2(μ-η 5-η 5-C 10H 8)] ( 4). The reaction of 3 with azobenzene, in wet toluene, gives [{Ti(η 5-C 5H 5)Cl}2(μ-O)(μ-η 5-η 5-C 10H 8)] ( 5) and 1,2-diphenyl hydrazine. The alkylation of 4 and the analogous zirconium complex [{Zr(η 5-C 5H 55)Cl 2} 2(μ-η 5-η 5-C 10H 8)] ( 2) with LiCH 2SiMe 3 or LiCH 3 permits isolation of the tetraalkyl derivatives [{M(η 5-C 5H 5)(CH 2SiMe 3) 2} 2(μ-η 5-η 5-C 10H 8)] (M  Ti ( 6); Zr ( 8)) and [{Ti(η 5-C 5H 5)(CH 3) 2} 2(μ-η 5-η 5C 10H 8)] ( 7). All the new fulvalene compounds were characterized by IR, and 1H and 13C NMR spectroscope, and mass spectra and 5 by X-ray diffraction. The structure of 5 is very similar to that of the comparable Ti IV compound [{Ti(η 5-C 5H 5) 2Cl} 2(μ-O)] except for the smaller TiOTi angle (159.4° against 173.81°) and a significant deviation from linearity.