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

The reaction of Ti(NMe(2))(4) with 2 equiv of Me(3)SiN(3) in toluene solution affords a dark red polymeric material of composition [Ti(NMe(2))(2)(N(3))(2)](n) (1). If the reaction is carried out in pyridine (py) solution, dark red, crystalline [Ti(NMe(2))(2)(N(3))(2)(py)(2)] (2) is formed. Analogous reactions of Ti(NMe(2))(4) with 2 or 1 equiv of Me(3)SiN(3) in the presence of 1 equiv of bipyridyl (bipy) in toluene solution afford brown crystals of [Ti(NMe(2))(2)(N(3))(2)(bipy)] (3) and dark red crystals of [Ti(NMe(2))(3)(N(3))(bipy)] (4), respectively. Crystallographic data for 2: orthorhombic, C222(1), a = 7.120(1) A, b = 15.899(3) A, c = 16.946(4) A, V = 1918.3(6) A(3), rho = 1.310 g/cm(3), Z = 4. Crystallographic data for 3: monoclinic, I2/a, a = 7.358(2) A, b = 16.808(4) A, c = 14.837(6) A, beta = 95.40(2) degrees, V = 1826.8(1) A(3), rho = 1.368 g/cm(3), Z = 4. Crystallographic data for 4: monoclinic, P2(1)/c, a = 15.682(2) A, b = 8.814(1) A, c = 15.128(1) A, beta = 108.39(1) degrees, V = 1984.2(4) A(3), rho = 1.267 g/cm(3), Z = 4. Compounds 1 and 2 deposit thin films of titanium nitride (TiN) on silica and/or nickel substrates in the temperature range 300-400 degrees C. The TiN films deposited from precursor 2 are superior to those deposited from 1.