Synthesis, structures, and DFT bonding analysis of new titanium hydrazido(2-) complexes

Area of Science:

• Organometallic Chemistry
• Coordination Chemistry
• Titanium Complexes

Background:

• Titanium hydrazido(2-) complexes represent a less explored area of titanium chemistry.
• Understanding the synthesis and bonding of these complexes is crucial for developing new catalytic and material applications.

Purpose of the Study:

• To synthesize novel monomeric and dimeric titanium hydrazido(2-) complexes.
• To investigate the structural characteristics and bonding modes of these complexes using X-ray crystallography and DFT calculations.
• To explore the reactivity of titanium hydrazido(2-) species with different ligands.

Main Methods:

• Synthesis of titanium hydrazido(2-) complexes via reactions of titanium precursors with hydrazine derivatives.
• Structural characterization using X-ray diffraction.
• Computational analysis using Density Functional Theory (DFT) to study electronic structure and bonding.

Main Results:

• Successful synthesis of monomeric terminal titanium hydrazido(2-) species and dimeric bridged compounds.
• X-ray structures revealed N-H...Cl hydrogen bonding in dimeric complexes.
• DFT calculations indicated analogous binding of hydrazido(2-) to terminal imido ligands, with destabilization due to N-beta lone pair interaction.

Conclusions:

• Compounds 1 and 4 serve as valuable precursors for terminal hydrazido(2-) chemistry.
• The electronic structure analysis provides insights into the sigma and pi donor abilities of hydrazido ligands compared to imido ligands.
• Bridging hydrazido ligands exhibit metallocyclic character through TiN2 interactions.