Cp2TiCl2 is a generally useful reagent that effectively behaves as a source of Cp2Ti2+. A large range of nucleophiles will displace chloride. With NaSH and with polysulfide salts, one obtains the sulfido derivatives Cp2Ti2 and Cp2TiS5. The Petasis reagent, Cp2Ti2, is prepared from the action of methylmagnesium chloride or methyllithium on Cp2TiCl2. This reagent is useful for the conversion of esters into vinyl ethers. The Tebbe reagent Cp2TiClAl2, arises by the action of 2 equivalents Al3 on Cp2TiCl2.
One Cp ligand can be removed from Cp2TiCl2 to give tetrahedral CpTiCl3. This conversion can be effected with TiCl4 or by reaction with SOCl2. Titanocene itself, TiCp2, is so highly reactive that it rearranges into a TiIII hydride dimer and has been the subject of much investigation. This dimer can be trapped by conducting the reduction of titanocene dichloride in the presence of ligands; in the presence of benzene, a fulvalene complex, can be prepared and the resulting solvate structurally characterised by X-ray crystallography. The same compound had been reported earlier by a lithium aluminium hydride reduction and sodium amalgam reduction of titanocene dichloride, and studied by 1H NMR prior to its definitive characterisation.
Reduction with zinc gives the dimer of bistitanium chloride in a solvent-mediated chemical equilibrium: Cp2TiCl2 is a precursor to TiII derivatives. Reductions have been investigated using Grignard reagent and alkyl lithium compounds. More conveniently handled reductants include Mg, Al, or Zn. The following syntheses demonstrate some of the compounds that can be generated by reduction of titanocene dichloride in the presence of π acceptor ligands: Alkyne derivatives of titanocene have the formula 2Ti and the corresponding benzyne complexes are known. One family of derivatives are the titanocyclopentadienes. Rosenthal's reagent, Cp2TiMe3, can be prepared by this method. Two structures are shown, A and B, which are both resonance contributors to the actual structure of Rosenthal's reagent. Titanocene equivalents react with alkenyl alkynes followed by carbonylation and hydrolysis to form bicyclic cyclopentadienones, related to the Pauson–Khand reaction). A similar reaction is the reductive cyclization of enones to form the corresponding alcohol in a stereoselective manner. Reduction of titanocene dichloride in the presence of conjugated dienes such as 1,3-butadiene gives η3-allyltitanium complexes. Related reactions occur with diynes. Furthermore, titanocene can catalyze C-C bond metathesis to form asymmetric diynes.
Derivatives of (C5Me5)2TiCl2
Many analogues of Cp2TiCl2 are known. Prominent examples are the ring-methylated derivatives 2TiCl2 and 2TiCl2. The ethylene complex2Ti can be synthesised by Na reduction of 2TiCl2 in the presence of ethylene. The Cp compound has not been prepared. This pentamethylcyclopentadienyl species undergoes many reactions such as cycloadditions of alkynes.
