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Chiral bis(η5:η1-pentafulvene)titanium complexes

The series of bis(pentafulvene)titanium complexes (η6-C 5H4=CR2)2Ti (=CR2 = C(p-tol)2 (3), adamantyl (4)) and their corresponding bis(benzofulvene) derivatives (η6-C9H 6=CR2)2Ti (=CR2 = C(p-tol) 2 (7), adamantyl (8)) have been synthesized by reaction of TiCl 3·3THF with the pentafulvene ligands (2 equiv) and magnesium as reducing agent (1.5 equiv). The bis(fulvene) complexes 7 and 8 have been obtained as diastereomerically pure compounds. All complexes have been characterized by spectroscopy and by single-crystal X-ray diffraction. The bonding situation is best described as a π-η5:σ- η1 coordination mode. The bis(fulvene) complex 3 is approximately C2 symmetric, whereas 7 crystallizes as a conglomerate in the monoclinic space group P21 and one of the enantiomers was identified as a (S,pS,pR) stereoisomer showing C1 symmetry. The adamantyl benzofulvene complex 8 crystallizes in the monoclinic space group P2 1/c; both benzofulvene ligands are coordinated as optical antipodes, and a (S,pS,pR)/(R,pR,pS) configuration is found in the solid state. Reaction of 3 and 7 with HCl/Et2O leads to the corresponding bis(cyclopentadienyl)titanium chlorides (η5-C5H 4-CHR2)2TiCl2 (R = p-tol (9)) and the bis(indenyltitanium) derivative (η5-C9H 6-CHR2)2TiCl2 (R = p-tol2 (10)).

Molecular structures of a series of substituted bis(η5-cyclopentadienyl)titanium dihalides CpR 2TiX2 [X = F, Cl, Br and I; R = CHPh2, CH(p-Tol)2 and adamantyl]

Metallocene dihalides and derivatives thereof are of great interest as precursors for catalysts in polymerization reactions, as antitumor agents and, due to their increased stability, as suitable starting materials in salt metathesis reactions and the generation of metallocene fragments. We report the synthesis and structural characterization of a series of eleven substituted bis(η5-cyclopentadienyl)titanium dihalides, namely bis[η5-1-(diphenylmethyl)cyclopentadienyl]difluoridotitanium(IV), [Ti(C18H15)2F2], bis{η5-1-[bis(4-methylphenyl)methyl]cyclopentadienyl}difluoridotitanium(IV), [Ti(C20H19)2F2], and bis{η5-1-[bis(adamantan-2-yl)methyl]cyclopentadienyl}difluoridotitanium(IV), [Ti(C15H19)2F2], together with the bromide and iodide analogues, and the chloride analogues of the diphenylmethyl and adamantyl complexes. These eleven complexes were prepared by the reaction of the corresponding bis(η5:η1-pentafulvene)titanium complexes with different hydrogen halides (Cl, Br and I). The titanocene fluorides become available via chloride–fluoride exchange reactions.