RT info:eu-repo/semantics/article T1 Fulvalene cyclopentadienyl titanium and zirconium(III) and zirconium(IV) complexes. X-Ray crystal structure of [{Ti(η5-C5H5)Cl}2(μ-O)( μ-η5- η5-C10H8)] A1 Cano Sierra, Ana María A1 Cuenca Agreda, Tomás A1 Rodríguez Centeno, Gema María A1 Royo Gracia, Pascual A1 Cardin, Christine J. A1 Wilcock, Deborah J. K1 Oxophilic transition metals K1 Tetravalent zirconium K1 Molecular structure K1 Titanocene K1 Chemistry K1 Derivatives K1 Trivalent K1 Oxidation K1 Bonds K1 Ciencia K1 Química inorgánica K1 Science K1 Chemistry, inorganic AB The reaction of the fulvalene titanium(III) hydride [{Ti(η5-C5H5)(μ-H)}2(μ-η5-η5-C10H8)] (1) with chlorine leads to [{Ti(η5-C5H5)(μ-Cl)}2(μ-η5-η5-C10H8)] (3) and [{Ti(η5-C5H5)Cl2}2(μ-η5-η5-C10H8)] (4). The reaction of 3 with azobenzene, in wet toluene, gives [{Ti(η5-C5H5)Cl}2(μ-O)(μ-η5-η5-C10H8)] (5) and 1,2-diphenyl hydrazine. The alkylation of 4 and the analogous zirconium complex [{Zr(η5-C5H55)Cl2}2(μ-η5-η5-C10H8)] (2) with LiCH2SiMe3 or LiCH3 permits isolation of the tetraalkyl derivatives [{M(η5-C5H5)(CH2SiMe3)2}2(μ-η5-η5-C10H8)] (M  Ti (6); Zr (8)) and [{Ti(η5-C5H5)(CH3)2}2(μ-η5-η5C10H8)] (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 TiIV compound [{Ti(η5-C5H5)2Cl}2(μ-O)] except for the smaller TiOTi angle (159.4° against 173.81°) and a significant deviation from linearity. PB Elsevier SN 0022-328X YR 1993 FD 1993 LK http://hdl.handle.net/10017/4607 UL http://hdl.handle.net/10017/4607 LA eng NO This work was supported by CICYT (PB89-0208)and EEC [SCl/0137-C(AM)]. A.C. gratefully acknowl­ edges CICYT and G.R. Repsol Quimica, s.a. for a fellowship. DS MINDS@UW RD 28-mar-2024