Reactions of permethyltitanocene tucked-in derivatives with carbon dioxide

Both single tucked-in permethyltitanocene 1 and double tucked-in permethyltitanocene 2 react with excess CO₂ by insertion into their Ti-CH₂ bonds. The former one precipitates instantly a yellow carboxylate-tethered oligomer [3] which is insoluble in aprotic solvents and in a vacuum it sublimes as a monomer without decomposition. Computations for n ≤ 4 optimised the structure of the monomer [3] and showed that open chain oligomers bound by dative O → Ti bonds were not sterically hindered. The latter bond dissociates when [3] is oxidized by chlorination with CDCl₃ or CD₂Cl₂ to give Ti(IV) chloride 4 or upon metathesis of [3] with Me₃SiCl yielding Ti(III) chloride 5. Oxidative addition of MeCN affords a C-C coupled dinuclear titanocene diimine 6. Compound [3] also reacts with 1 to give the tethered carbodiolate 8 or with [Cp*₂TiH] (where Cp* = η⁵-C₅Me₅) to give the half-tethered carbodiolate 10. The non-tethered carbodiolate 12 was obtained from [Cp*₂TiH] and CO₂ yielding titanocene formate by reaction of the latter with another equivalent of [Cp*₂TiH]. All these carbodiolates contain Ti(III) metal atoms forming electronic triplet states of axial or orthorhombic symmetry. In contrast to the rapidly reacting 1 compound 2 reacts with excess CO₂ slowly in m-xylene at 100 °C using only one of its two Ti-CH₂ moieties. The structure of the obtained carbodiolate 13 indicates that the primary product analogous to 3 reacts with 2 more rapidly than with CO₂.