The structure and chemistry of tris(pentafluorophenyl)borane protected mononuclear nitridotitanium complexes

Area of Science:

• Organometallic Chemistry
• Inorganic Chemistry
• Materials Science

Background:

• Titanium amide complexes are versatile precursors in synthesis.
• Understanding ligand exchange and activation is crucial for developing new catalytic systems.
• Boron-nitrogen compounds offer unique electronic and structural properties.

Purpose of the Study:

• To investigate the reaction of titanium amide with a boron-nitrogen adduct.
• To characterize the resulting titanium-nitrogen anion and its salts.
• To explore the electronic structure and reactivity of the novel titanium complex.

Main Methods:

• Treatment of TiCl(NMe(2))(3) with H(3)N·B(C(6)F(5))(3).
• Cation exchange reactions with various ammonium and phosphonium chlorides.
• X-ray crystallography for structural determination.
• Density Functional Theory (DFT) calculations for electronic structure analysis.

Main Results:

• Formation of a structurally characterized salt containing a [Ti≡NB(C(6)F(5))(3)(Cl)(2)(NMe(2)H)(2)](-) anion.
• Retention of trigonal bipyramidal geometry in the anion across different salts.
• DFT calculations confirm Ti-N triple bond character and Ti-N π-bonding in frontier orbitals.
• Ligand substitution studies reveal reactivity with pyridine and 2,2'-bipyridyl.

Conclusions:

• The reaction successfully achieved N-H activation and formation of a Ti-N triple bond.
• The novel titanium-nitrogen anion exhibits structural and electronic stability.
• The complex displays tunable reactivity towards different ligands, leading to diverse coordination geometries.