A nitrido salt reagent of titanium

Area of Science:

• Organometallic Chemistry
• Inorganic Chemistry
• Materials Science

Background:

• Titanium imido complexes are versatile precursors in inorganic synthesis.
• The synthesis of molecular titanium nitrides is challenging and less explored.
• Sterically demanding ligands like (tBu)nacnac can stabilize reactive metal centers.

Purpose of the Study:

• To synthesize and characterize a rare dimeric titanium nitride complex.
• To explore the reactivity of a parent titanium imido complex with aluminum and boron reagents.
• To investigate the structural diversity of titanium-nitrogen compounds.

Main Methods:

• Deprotonation of a titanium imido complex using potassium benzyl.
• Isolation and structural characterization of the titanium nitride dimer via X-ray crystallography.
• Reaction of the titanium imido complex with aluminum and boron electrophiles.

Main Results:

• A rare dimeric molecular titanium nitride, {[K][((tBu)nacnac)Ti≡N(Ntolyl2)]}2, was successfully synthesized.
• The parent titanium imido complex yielded an aluminylimido-etherate adduct, ((tBu)nacnac)Ti≡N[AlMe2(OEt2)](Ntolyl2), upon reaction with an aluminum reagent.
• A borylimido derivative, ((tBu)nacnac)Ti═NBEt2(Ntolyl2), was also obtained from the parent imido complex.

Conclusions:

• The parent titanium imido complex serves as a valuable precursor for synthesizing unique titanium nitride and imido derivatives.
• The study expands the known chemistry of titanium-nitrogen multiple bonds.
• Steric bulk of the (tBu)nacnac ligand is crucial for stabilizing these novel titanium complexes.