title: Monomeric Titanium(IV) Azides as a New Route to Titanium Nitride.
abstract: 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) Å, b = 15.899(3) Å, c = 16.946(4) Å, V = 1918.3(6) Å(3), rho = 1.310 g/cm(3), Z = 4. Crystallographic data for 3: monoclinic, I2/a, a = 7.358(2) Å, b = 16.808(4) Å, c = 14.837(6) Å, beta = 95.40(2) degrees, V = 1826.8(1) Å(3), rho = 1.368 g/cm(3), Z = 4. Crystallographic data for 4: monoclinic, P2(1)/c, a = 15.682(2) Å, b = 8.814(1) Å, c = 15.128(1) Å, beta = 108.39(1) degrees, V = 1984.2(4) Å(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.
authors.affiliation: Department of Chemistry & Biochemistry, The University of Texas at Austin, Austin, Texas 78712, Center for Materials Chemistry, The University of Texas at Austin, Austin, Texas 78712, and Institut für Anorganische Chemie der Universität, Tammannstrasse 4, D-37077, Göttingen, Germany.
authors.forename: Claire J.
authors.initials: CJ
authors.lastname: Carmalt
authors.forename: Alan H.
authors.initials: AH
authors.lastname: Cowley
authors.forename: Robert D.
authors.initials: RD
authors.lastname: Culp
authors.forename: Richard A.
authors.initials: RA
authors.lastname: Jones
authors.forename: Yang-Ming
authors.initials: YM
authors.lastname: Sun
authors.forename: Bill
authors.initials: B
authors.lastname: Fitts
authors.forename: Sandra
authors.initials: S
authors.lastname: Whaley
authors.forename: Herbert W.
authors.initials: HW
authors.lastname: Roesky