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.

Atmospheric Pressure Chemical Vapour Deposition of TiCl4 and tBuAsH2 to Form Titanium Arsenide Thin Films

“…TiCl 4 /NH 3 ) and singlesource precursors, such as amido and imido titanium(IV) compounds. [4][5][6][7] Additionally, we have used silylamines and azides as precursors, which resulted in high quality TiN films, [8][9][10] and this methodology can be extended to other transition metal nitrides. [11] As the understanding of the roles of the precursor have developed, more user-friendly (i.e.…”

The Binary Group 4 Azides [Ti(N3)4], [P(C6H5)4][Ti(N3)5], and [P(C6H5)4]2[Ti(N3)6] and on Linear TiNNN Coordination

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Whereas numerous partially azide-substituted titanium compounds had been reported, [1][2][3][4][5][6][7] no binary Group 4 azides were known. In a recent theoretical study, the Group 4 metal tetrazides [M(N 3 ) 4 ] (M = Ti, Zr, Hf, Th) were predicted [8] to be vibrationally stable, exhibiting tetrahedral structures with unique linear M À N À NN bond angles (see Figure 1).

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Molecular Dynamics Study of Laser and Plasma Nitriding of Titanium

“…Pix',y')dx'dy' 2nkR (2) ro= 300K (room-temperature),i? = y{x -x'f+{y -y'f+z^, a = v/2b, b = k/pi^C is the material diffusion coefficient, k is the material heat conductivity coefficient, PM is the density of the material, and c is the heat capacity of the material.…”

“…The interesting properties of titanium nitride, such as its high hardness, excellent conductivity, and good corrosion resistance and temperature stability, are very attractive for advanced technological applications [1][2][3]. On the other hand, titanium and titanium alloys have numerous industrial applications due to their high strength-to-weight ratio, good heat treatment capability, low density, and good biocompatibility.…”