Titanium redox with complexes

VIV. As with the titanium porphyrins, these complexes occur as vanadyl complexes with an axial oxo group and produce a "normal electronic spectrum which changes to a hematin spectrum when trifluoroacetic acid is added [Bonnett (9)]. The vanadyl porphyrins contain a single unpaired electron (/i=l,4B.M.) and their esr spectra have been studied in some detail [Kivelson (113a), Roberts (152)]. The rich redox chemistry of the inorganic vanadium salts is not reflected in the vanadyl porphyrins, where the +4 state seems to be exceptionally stable. 

The advantages of titanium complexes over other metallic complexes is high selectivity, which can be readily adjusted by proper selection of ligands. Moreover, they are relative iaert to redox processes. The most common synthesis of chiral titanium complexes iavolves displacement of chloride or alkoxide groups on titanium with a chiral ligand, L ... 

Keeping in mind the above studies of multivalent cations (Fe, Cr and Mn) in aqueous medium, some experiments involving redox or complexometric reactions of these metal ions have been carried out, using ultrasound (20 kHz) and its effect on the precipitation, oxidation, reduction and decomposition of complex have been evaluated. An Ultrasonic Processor model P2 with a titanium tip of diameter 12 mm and 250 watts power was used. In the subsequent sections details of some of the interesting experiments, carried out in aqueous solutions of salts of Fe, Cr and Mn in their different oxidation states, have been discussed. 

Photovoltaic cells based on the sensitization of mesoporous titanium dioxide by Ru(II) complex dyes in conjunction with the I.3 /U redox couple as a mediator have proved very efficient at exploiting this principle. In such systems, the ionic mediator travels back and forth by diffusion from the working electrode to the counterelectrode, to shuttle to the sensitizer the electrons that have gone through the electrical circuit [18, 21, 84]. Recently, solid-state devices have been described where the liquid electrolyte present in the pores of the nanocrystalline oxide film is replaced by a large-bandgap p-type semiconductor acting as a hole-transport medium [85 88]. 

Hydrolysis, redox, metathetical, and halide abstraction reactions are covered here. Some of these reactions lead to specific complexes with Ti-O, Ti-N, and Ti-C bonds which are described in subsequent sections. Comments on the applications of the mono-Cp trihalo titanium complexes as olefin polymerization pre-catalysts have been mentioned in Section 4.05.3.1.1 and some recent advances in this field are also considered here. (See Chapter 4.09 of this work.)... 

Recent results in the field of catalytic oxidations with hydrogen peroxide are reviewed. Most effective catalysts fall into three categories metallorganic compounds, phase-transfer catalysts, redox zeolites. Metalloporphyrins and Pt-phosphine complexes are representative of first category. Mo and W polyoxome-talates and related systems, in association with phase transfer agents, belong to the second one. Titanium silicalite (TS-1) is the most studied redox zeolite. The oxidation of nitrogen and sulphur compounds and Fenton-like reactions are not reviewed. 

One approach to creating heterogeneous oxidation catalysts with novel activities and selectivities is to incorporate redox metals, by isomorphous substitution, into the lattice framework of zeolites and related molecular sieves. Site-isolation of redox metals in inorganic lattices prevents the dimerization or oligomerization of active oxometal species which is characteristic of many homogeneous oxometal complexes and leads to their deactivation in solution. We coined the term redox molecular sieves to describe such catalysts . The first and most well-known example is titanium silicalite (TS-1) which has been shown to catalyze a variety of systhetically useful oxidations with H202. ... 

Although the radicals formed in the reactions of HjOa with Fe", Fe" , and Ce " have been identified, it has been shown that on addition of other metal ions to these redox systems, similar e.s.r. spectra are recorded but the intensity of the signal is dependent on the concentration of the metal ion present. In the presence of ZrO +, Hf +, Th +, and U02 +, it would appear that these transition-metal ions in their highest oxidation states form complexes with the free-radical species generated. Relative rate constants have been measured for reactions of hydroxy-radicals formed in the Fe" and Ti " redox systems. Although in the case of titanium(iii) the TiOO + radical is formed, it is suggested that the FeOH+ ions react with peroxide to produce the ferryl ion as an intermediate... 

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