Titanium atom

In this oxidation state the titanium atom has formally lost its 3d and 4s electrons as expected, therefore, it forms compounds which do not have the characteristics of transition metal compounds, and which indeed show strong resemblances to the corresponding compounds of the lower elements (Si, Ge, Sn, Pb) of Group IV—the group into which Mendeleef put titanium in his original form of the periodic table. 

This occurs naturally as a white solid in various crystalline forms, in all of which six oxygen atoms surround each titanium atom. Titanium dioxide is important as a white pigment, because it is nontoxic. chemically inert and highly opaque, and can be finely ground for paint purposes it is often prepared pure by dissolving the natural form in sulphuric acid, hydrolysing to the hydrated dioxide and heating the latter to make the anhydrous form. 

The monometallic mechanism is illustrated in Fig. 7.13a. It involves the monomer coordinating with an alkylated titanium atom. The insertion of the monomer into the titanium-carbon bond propagates the chain. As shown in... 

Figure 7.14a illustrates the insertion of a propylene monomer into an edge vacancy in a crystal adjacent to an alkylated titanium atom. In Fig. 7.14b a cross-sectional view of the same site shows how the preferential orientation of the coordinated monomer is dictated by constraints imposed by the protuberances on the crystal surface. 

Heterogeneous Catalysis. The main discovery of the 1980s was the use of titanium sihcaUte (TS-1) a synthetic zeoHte from the ZSM family containing no aluminum and where some titanium atoms replace siUcon atoms in the crystalline system (Ti/Si = 5%) (33). This zeoHte can be obtained by the hydrolysis of a siUcate and an alkyl titanate in the presence of quaternary ammonium hydroxide followed by heating to 170°C. Mainly studies have been devoted to the stmcture of TS-1 and its behavior toward H2O2 (34). The oxidation properties of the couple H2O2/TS-I have been extensively developed in... 

Stmctures are highly varied among the transition metals. The titanium atom in titanium tetraethoxide has the coordination number 6 (Fig. 1). The corresponding zirconium compound, with coordination number 8, has a different stmcture (Fig. 2). Metal alkoxides are colored when the corresponding metal ions are colored, otherwise they are not. 

Titanium Trifluoride. The trifluoride (121) is a blue crystalline soHd, density 2980 kg/m, ia which the titanium atoms are six-coordinate at the center of a slightly distorted octahedron, where the mean Ti—F distance is 197 pm. Titanium trifluoride [13470-08-1] is stable ia air at room temperature but decomposes to titanium dioxide when heated to 100°C. It is insoluble ia water, dilute acid, and alkaUes but decomposes ia hot concentrated acids. The compound sublimes under vacuum at ca 900°C but disproportionates to titanium and titanium tetrafluoride [7783-63-3] at higher temperatures. 

Titanium Dichloride. Titanium dichloride [10049-06-6] is a black crystalline soHd (mp > 1035 at 10°C, bp > 1500 at 40°C, density 31(40) kg/m ). Initial reports that the titanium atoms occupy alternate layers of octahedral interstices between hexagonaHy close-packed chlorines (analogous to titanium disulfide) have been disputed (120). TiCl2 reacts vigorously with water to form a solution of titanium trichloride andUberate hydrogen. The dichloride is difficult to obtain pure because it slowly disproportionates. 

The 1-alkoxytitatranes can be synthesized by the reaction of equimolar amounts of tetraalkyl titanates and triethanolamine (105). X-ray crystallographic analysis of the soHd isolated from the reaction of one mole of triethanolamine and one mole of TYZOR TPT confirms the stmcture as a centrosymmetric dimer having a Ti isopropoxy nitrilotriethoxy ratio of 1 1 1. The titanium atoms have achieved a coordination number of six via a rather unsymmetrical titanium—oxygen bridge (106). 

An acylate group is potentially a bidentate ligand. It may bond once or twice to one titanium, or bridge two titanium atoms as shown. 

Finally, the use of the constant pressure minimization algorithm allows searching for phenomena that can be considered as precursors of pressure-induced transitions. For example, the predicted behaviour of the anatase cell constants as a function of pressure shows that the a(P) and c(P) plots are only linear for P<4 GPa, the value that is close to both the theoretical and experimental transition pressures. At higher pressures the a constant starts to grow under compression, indicating inherent structural instability. In the case of ratile there is a different precursor effect, nami y at 11 GPa the distances between the titanium atom and the two different oxygens, axial and equatorial, become equal. Once again, the pressure corresponds closely to the phase transition point. 

In the perfect lattice the dominant feature of the electron distribution is the formation of the covalent, directional bond between Ti atoms produced by the electrons associated with d-orbitals. The concentration of charge between adjacent A1 atoms corresponds to p and py electrons, but these electrons are spatially more dispersed than the d-electrons between titanium atoms. Significantly, there is no indication of a localized charge build-up between adjacent Ti and A1 atoms (Fu and Yoo 1990 Woodward, et al. 1991 Song, et al. 1994). The charge densities in (110) planes are shown in Fig. 7a and b for the structures relaxed using the Finnis-Sinclair type potentials and the full-potential LMTO method, respectively. 

A new process developed by Institut Francais du Petrole produces butene-1 (1-butene) by dimerizing ethylene.A homogeneous catalyst system based on a titanium complex is used. The reaction is a concerted coupling of two molecules on a titanium atom, affording a titanium (IV) cyclic compound, which then decomposes to butene-1 by an intramolecular (3-hydrogen transfer reaction. ... 

Fig. 1. The structure of rutile. Large circles represent the centers of titanium atoms, small circles those of oxygen atoms. One octahedron with oxygen atoms at its cornex and a titanium atom at its center is shown two of its edges, those indicated by arrows, are shared with adjoining octahedra.

Brookite is composed of octahedra, each with a titanium atom at its center and oxygen atoms at its corners. 

The suggested structure places eight titanium atoms and two groups of eight oxygen atoms each in the positions 8c, with three sets of... 

The structure found for brookite is that shown in Fig. 5. Each titanium atom is surrounded by six oxygen atoms and each oxygen by three titanium atoms. The various interatomic distances, given in Table VII, are similar to those in rutile and anatase for example, the average titanium-oxygen distance is 1,95 A. The oxygen-oxygen distances and the distortion of the basic octahedra have been discussed in the previous sections in the course of derivation of the structure. 

Titanium atoms have been cocondensed with CO and N2 matrices (138) and the products identified as TitCOlg and Ti(N2)e. The IR data... 

Transition-metal atoms have been shown to deoxygenate epoxides to alkenes (36). Chromium and titanium atoms emerged as the most effective species in this regard, abstracting over two equivalents of oxygen. By studying the reaction of a wide range of epoxides with chromium atoms, the reaction... 

Both types of complex are extremely air-sensitive and are paramagnetic, with one unpaired electron per titanium atom. Their formulation as monomeric, symmetrical, bidentate, chelate complexes, (IV) and (V), has been established from spectral, magnetic, and molecular-weight data. 

Ti A neutral titanium atom has 22 electrons. The ground-state configuration is (Ar] A 3 cf. The spins of the 4 electrons cancel, but the two electrons in 3 orbitals have the same spin orientation, so... 

Fig. 6.4 Layered structure of LixTiSa, showing the lithium ions between the TiSa sheets. This is an anion close-packed lattice in which alternate layers between the anion sheets are occupied by a redox-active titanium atom. Lithium inserts itself into the empty remaining layers. (Adapted from [68])...

TiCRjtftc) was prepared starting from Ti(NR2)4 4,5) or TiCl4 (6). The structure of the ethyl compound was elucidated by X-ray studies (7, S). The titanium atom is eight-coordinated by the sulfur atoms of the four chelating ligands and the coordination geometry closely approximates to that of a dodecahedron. 

A the titanium atoms are not equal on both sides of the equation... 

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