Synthesis, characterization and functionalization of titanium κ amidinato complexes from carbodiimides.

A series of titanium amidinato complexes were synthesized by stoichiometric insertion reactions of carbodiimides into bis(π-η:σ-η-pentafulvene)titanium complexes. NMR studies and single-crystal X-ray diffraction showed κ coordination of the former carbodiimides to the metal center. DFT calculations were performed, confirming the clear preference for a single nitrogen atom coordinating to the metal center with a high energy transition state for the formation of a chelating heteroallyl ligand.

From Coordination to Noncoordination: Syntheses and Substitution Lability Studies of Titanium Triflato Complexes.

A new concept for obtaining cationic complexes with triflate counteranions from coordinating triflato ligands was developed. Various routes are leading to titanium(IV) and titanium(III) triflato complexes efficiently. The reactions of pentafulvene titanium complexes with either triflic acid or silver triflate give the corresponding titanium(IV) triflato complexes in excellent yields.

Syntheses, Characterization, and Redox Activity of Ferrocene-Containing Titanium Complexes.

The chemistry of bis(π-η:σ-η-pentafulvene)titanium complexes is characterized by a broad range of E-H activation and Ti-C functionalization reactions, whereas ferrocene derivatives are easily accessible and redox-active compounds. The reaction of ferrocenealdehyde and -ketones with bis(π-η:σ-η-pentafulvene)titanium complexes result in the formation of bimetallic complexes via insertion of the C=O double bond of the aldehyde/ketone into the Ti-C bond of the pentafulvene moiety. The reaction of bis(π-η:σ-η-pentafulvene)titanium complexes with ferrocenyl alcohols leads to alcoholate complexes via deprotonation of the OH group by the pentafulvene ligand.

Syntheses, Characterization, and Multifaceted Coordination Chemistry of Hydrazonido Titanium Complexes.

The reaction of hydrazones with bis(π-η:σ-η-pentafulvene)titanium complexes leads to both hydrazonido and hydrazido complexes depending on the interaction of the hydrazone with the fulvene ligand of the metal complex. The molecular structures mostly reveal κ, side-on coordination of the hydrazonido ligand due to the deprotonation of the N-H bond by one of the fulvene moieties. Instead of deprotonation, the reaction of the bis(adamantylidene fulvene)titanium complexes with cinnamon aldehyde phenylhydrazone leads to κ coordination.

Titanium-Catalyzed Polymerization of a Lewis Base-Stabilized Phosphinoborane.

The reaction of the Lewis base-stabilized phosphinoborane monomer tBuHPBH NMe (2 a) with catalytic amounts of bis(η :η -adamantylidenepentafulvene)titanium (1) provides a convenient new route to the polyphosphinoborane [tBuPH-BH ] (3 a). This method offers access to high molar mass materials under mild conditions and with short reaction times (20 °C, 1 h in toluene). It represents an unprecedented example of a transition metal-mediated polymerization of a Lewis base-stabilized Group 13/15 compound.