Molecular nitrides with titanium and Group 13-15 elements.

Area of Science:

• Inorganic Chemistry
• Organometallic Chemistry
• Materials Science

Background:

• Titanium imido-nitrido complexes serve as versatile precursors in coordination chemistry.
• The synthesis of heterometallic nitrido complexes is crucial for developing new materials with unique electronic and catalytic properties.
• Understanding the reactivity of titanium imido-nitrido complexes with main group element amides is key to expanding synthetic methodologies.

Purpose of the Study:

• To explore the reactivity of the imido-nitrido titanium complex [{Ti(eta(5)-C(5)Me(5))(mu-NH)}(3)(mu(3)-N)] (1) with amido derivatives of Group 13-15 elements.
• To synthesize and characterize novel heterometallic nitrido complexes with diverse structural architectures.
• To investigate the influence of different main group elements (Al, Ga, In, Ge, Sn, Pb, Sb, Bi) on the resulting complex structures.

Main Methods:

• Reaction of the titanium complex (1) with various amido derivatives of aluminum, gallium, indium, germanium, tin, lead, antimony, and bismuth.
• Utilized high-temperature reactions in toluene and room temperature reactions for complex synthesis.
• Employed Nuclear Magnetic Resonance (NMR) spectroscopy for reaction monitoring and intermediate identification.
• Determined the X-ray crystal structures of key synthesized compounds.

Main Results:

• Synthesized a series of heterometallic nitrido complexes, including single-cube amidoaluminum complex (2) and corner-shared double-cube compounds (3-4, 11-13).
• Observed the formation of a unique gallium-gallium bonded complex (5) and cube-type complexes with Ge, Sn, and Pb (6-8).
• Identified reaction intermediates in the formation of tin complexes (9-10) and characterized a singular aluminum-titanium square-pyramidal aggregate (14).

Conclusions:

• The imido-nitrido titanium complex (1) is a highly versatile precursor for constructing diverse heterometallic nitrido architectures.
• The nature of the main group element significantly influences the resulting complex's structure, leading to varied cube-type arrangements.
• The study expands the synthetic scope of heterometallic nitrido complexes and provides insights into their structural diversity.