Monomeric Titanium(IV) Azides as a New Route to Titanium Nitride.

The reaction of Ti(NMe2)4 with 2 equiv of Me3SiN3 in toluene solution affords a dark red polymeric material of composition [Ti(NMe2)2(N3)2]n (1). If the reaction is carried out in pyridine (py) solution, dark red, crystalline [Ti(NMe2)2(N3)2(py)2] (2) is formed. Analogous reactions of Ti(NMe2)4 with 2 or 1 equiv of Me3SiN3 in the presence of 1 equiv of bipyridyl (bipy) in toluene solution afford brown crystals of [Ti(NMe2)2(N3)2(bipy)] (3) and dark red crystals of [Ti(NMe2)3(N3)(bipy)] (4), respectively. Crystallographic data for 2:  orthorhombic, C2221, a = 7.120(1) A, b = 15.899(3) A, c = 16.946(4) A, V = 1918.3(6) A3, ρ = 1.310 g/cm3, Z = 4. Crystallographic data for 3:  monoclinic, I2/a, a = 7.358(2) A, b = 16.808(4) A, c = 14.837(6) A, β = 95.40(2)°, V = 1826.8(1) A3, ρ = 1.368 g/cm3, Z = 4. Crystallographic data for 4:  monoclinic, P21/c, a = 15.682(2) A, b = 8.814(1) A, c = 15.128(1) A, β = 108.39(1)°, V = 1984.2(4) A3, ρ = 1.267 g/cm3, Z = 4. Compounds 1 and 2 deposit thin films of titanium nitrid...