Titanium complexes alkoxides

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 ... 

Titanium, tetrakis(trimethysilyl)oxy-, 3, 334 Titanium, tetranitrato-stereochemistry, 1,94 Titanium, triaquabis(oxalato)-structure, I, 78 Titanium, tris(acetylacetone)-structurc, 1,65 Titanium alkoxides oligomeric structure, 2,346 synthesis ammonia, 2, 338 Titanium chloride photographic developer, 6,99 Titanium complexes acetylacetone dinuclear, 2, 372 alkyl... 

Chae, H. K. Payne, D. A. Xu, Z. Ma, L. 1994. Molecular structure of a new lead titanium bimetallic alkoxide complex [PbTi2( t4-0)(00CCH3)(0CH2CH3)7]2 Evolution of structure on heat treatment and the formation of thin-layer dielectrics. Chem. Mat. 6 1589-1592. 

The proposed reaction mechanism is shown in Figure 2 8. First, a chiral titanium complex (/ )- 40 is formed by the exchange of two titanium alkoxides. 

Titanium Alkoxides Silica-supported titanium(IV) alkoxides and Ti-silicalite are industrial epoxidation catalysts [53-56] and have been applied in deperoxidation reactions [57]. Computational and EXAFS data [53, 54] as well as spectroscopic investigations on the surface species [58] have indicated that the dominant active surface species is a four-coordinate trisUoxy complex [(=SiO)3TiOH] [59] whose coordination shell expands to six-coordinate during catalysis [60]. 

Indeed, several interesting procedures based on three families of active catalysts organometallic complexes, phase-transfer compounds and titanium silicalite (TS-1), and peroxides have been settled and used also in industrial processes in the last decades of the 20th century. The most impressive breakthrough in this field was achieved by Katsuki and Sharpless, who obtained the enantioselective oxidation of prochiral allylic alcohols with alkyl hydroperoxides catalyzed by titanium tetra-alkoxides in the presence of chiral nonracemic tartrates. In fact Sharpless was awarded the Nobel Prize in 2001. 

In [1677] complex alkoxides and alkoxide-carboxylates were compared as precursors for preparation ofBST films. In contrast to the introduction of alkaline earth carboxylates in the form of preliminary isolated salts, in this work metal alkoxide solution in methoxyethanol containing titanium and alkaline-earth metal was modified by addition of 2-ethylhexanoic acid with subsequent slow distilling off the solvent and repeated dilutions with fresh portions of methoxyethanol. During the distillation process, part of the alkoxide groups are substituted by the 2-ethylhexanoate ligands. The exchange reaction of Ti(OPr )4 with acid was studied in different solvents, and it was demonstrated that in the course of distillation the titanium oxoisopropoxy-2-ethylhexanoate is formed with elimination of ester ... 

The asymmetric oxidation of sulphides to chiral sulphoxides with t-butyl hydroperoxide is catalysed very effectively by a titanium complex, produced in situ from a titanium alkoxide and a chiral binaphthol, with enantioselectivities up to 96%342. The Sharpless oxidation of aryl cinnamyl selenides 217 gave a chiral 1-phenyl-2-propen-l-ol (218) via an asymmetric [2,3] sigmatropic shift (Scheme 4)343. For other titanium-catalysed epoxidations, see Section V.D.l on vanadium catalysis. 

Now the aldol reaction can occur the positive charge on the titanium-complexed carbonyl oxygen atom makes the aldehyde reactive enough to be attacked even by the not very nucleophilic silyl enol ether. Chloride ion removes the silyl group and the titanium alkoxide captures it again. This last step should not surprise you as any alkoxide (MeOLi for example) will react with Me3SiCl to form a silyl ether. 

The essence of titanium-catalyzed asymmetric epoxidation is illustrated in Figure 1. As shown there, the four essential components of the reaction are the allylic alcdiol substrate, a titanium(IV) alkoxide, a chiral tartrate ester and an aUcyl hydroperoxide. The asynunetric complex formed from these reagents de-... 

Two aspects of stoichiometry are important in an asymmetric epoxidation one is the ratio of titanium to tartrate used for the catalyst and the other is the ratio of catalyst to substrate. With regard to the catalyst, it is crucial to obtaining the highest possible enantiomeric excess that at least a 10% excess of tartrate ester to titanium(IV) alkoxide be used in all asynunetric epoxidations. This is important when the reaction is being done with either a stoichiometric or a catalytic quantity of the complex. There appears to be no need to increase the excess of tartrate ester beyond 10-20% and, in fact, a larger excess has been shown to slow the epoxidation reaction unnecessarily. ... 

Most precursors used for titanium oxide preparation, especially for film production, are based on titanium alkoxides. A variety of mixed enolate-aUcoxide titanium complexes exist, such as 26a-f, 27, 28 and 29a-e, which are typical CVD precursors for titanium oxide. 

Many soluble catalysts are known which will polymerize ethylene and butadiene. High activity soluble catalysts are employed commercially for diene polymerization but most soluble types are inefficient for olefin polymerization. A few are crystalline and of known structure such as blue (7r-C5H5)2TiCl. AlEtaCl [49] and red [(tt-CsHs )2TiAlEt2 ] 2 [50]. The complex (tt-CsHs )2TiCl2. AlEt2Cl polymerizes ethylene rapidly but decomposes quickly to the much less active blue trivalent titanium complex. Soluble catalysts are obtained from titanium alkoxides or acetyl acetonates with aluminium trialkyls and these polymerize ethylene and butadiene. Several active species have been identified, dependent on the temperature of formation and the Al/Ti ratio. Reduction to the trivalent state is slow and incomplete and maximum activity for ethylene polymerization occurs at about 25% reduction to Ti [51]. 

Mixed-metal alkoxide complexes of thallium are also known. For example, Sn(/u-t-BuO)3Tl has both Sn(II) and T1(I) ions." The thallium site is unreactive as a donor for metal carbonyls. However, as indicated earlier, the indium(I) site of the indium analogue shows Lewis-base character. The Sn(IV)/Tl(I) mixed alkoxide [Sn(EtO)eTl2] exists as a one-dimensional polymer. This adduct reacts quantitatively with SnCl2 to form the homoleptic, mixed-valent [Sn2(OEt)6]n. Thallium-titanium double alkoxides have been synthesized using thallium alkoxide as one of the starting materials. ... 

Another efficient process has been described for the silylcyanation of aldehydes in the presence of salen-titanium alkoxide complexes [86]. When a chiral C2 symmetric bis(dihydrooxazole)-Mg complex is employed with aldehydes as substrates, both excellent chemical yields and enantiomeric excesses are obtained [87]. Chiral titanium complexes are also derived from optically active sulfoxi-mines and a titanium alkoxide precursor [88]. 

Titanium complexes containing methylsalicylate, phenolphthalein,522 furoic acid, isotan and picolinic acid ligands have been described.523 Keto alkoxide complexes such as TiCl3(02C6Fl7)524 and various maltolato derivatives525,526 have been prepared and characterized. 

Group 4 metals have also been used widely in conjunction with salen-type ligands (Figure 25). In 2006 Gregson et reported several chiral and achiral titanium salen alkoxide complexes for the ROP of lactide. All catalysts reported were modestly active and heteroselective (P 0.51-0.57). Several achiral Ti and Zr salan catalysts were reported by Gendler et for melt polymerization of lactide. While no stereoselectivity has been reported for either system, the Zr complexes were more active towards lactide ROP than the Ti analogs. 

The overall catalytic cycle is believed to involve various titanium complexes which all have at least one isopropoxy ligand attached to the metal (Scheme 1). Given this fact, it is evident that kind and structure of the alkoxide can influence the catalysis, in particular the chirality transfer step (4—>5, via 2) and the displacement of the product sulfoxide from 5 to regenerate 3. Evidence for this assumption was obtained in studies with both other titanium alkoxides and alcohols such as methanol. In all cases less efficient catalyst systems resulted. 

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