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) 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.
Carmalt
Claire J.
CJ
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.
Cowley
Alan H.
AH
Culp
Robert D.
RD
Jones
Richard A.
RA
Sun
Yang-Ming
YM
Fitts
Bill
B
Whaley
Sandra
S
Roesky
Herbert W.
HW