Zirconium complexes continued

The trimethylsilylated silicic acids formed in this instance are soluble in conventional organic solvents, and their volatility is sufficiently high for them to be analysed by gas chromatography. Carzo and Hoebbel [411] carried out a comprehensive study of the chromatographic retention of various trimethylsilylated silicic acids on different stationary phases Apiezon L and silicone OV-1 and OV-17. The analysis of metals in the form of volatile complexes continues to attract attention, and have been described for analysing sodium [412], potassium [412], radium [413], caesium [413], barium [414], calcium [414], strontium [415], beryllium [416, 417], magnesium [418], zinc [419, 420], nickel [419], mercury [421], copper [422, 423], silver [424, 425], cadmium [421], indium [426, 427], g ium [428], scandium [217], cobalt [421], thallium [426], hafnium [429, 430], lead [431, 432], titanium [430], vanadium [433], chromium [434-436], manganese [426], iron [437], yttrium [438], platinum [439,440], palladium [439, 441, 442], zirconium [430], molybdenum [443], ruthenium [444], rhodium [445], rare earths [446—449], thorium [221, 450, 451] and uranium [221, 452]. The literature on GC analysis of metal chelates was reviewed by Sokolov [458]. 

The first carbonitride alloys based on Ti(C,N)—Ni—Mo were iatroduced ia 1970 foUowed by (Ti, Mo)(C,N)-based compositions having fine microstmctures that provided a balance of wear resistance and toughness (4). Continued research on the titanium carbonitride alloys, often called TiC—TiN cermets, ia the 1980s led to the developmeat of complex cermets having a variety of additives such as molybdeaum carbide(2 l) [12069-89-5] M02C, TaC, NbC, zirconium carbide [12020-14-3], ZrC, hafnium carbide [12069-85-1], HfC, WC, vanadium carbide [12070-10-9], VC, chromium carbide (3 2)... 

Concomitant with continued olefin insertion into the metal-carbon bond of the titanium-aluminum complex, alkyl exchange and hydrogen-transfer reactions are observed. Whereas the normal reduction mechanism for transition-metal-organic complexes is initiated by release of olefins with formation of hydride followed by hydride transfer (184, 185) to an alkyl group, in the case of some titanium and zirconium compounds a reverse reaction takes place. By the release of ethane, a dimetalloalkane is formed. In a second step, ethylene from the dimetalloalkane is evolved, and two reduced metal atoms remain (119). 

Cyclopropane activation continues to be reported across the transition series. Consistent with earlier results, the insertion of zirconium(ll) into a methylenecyclopropane provides the a-methylenezirconacyclobutane complexes 168. An intermediate Zr(ll) methylenecyclopropane complex is isolated from the reaction of the parent zirconocene complex, but no intermediate is observed using the more reactive bis(indenyl) template (Equation 88) <2002JOM288>. 

High-coordination-number complexes of 0-keto-enolates continue to be obtained with the metals such as zirconium(IV),8 hafnium(IV),8 cerium(IV),9 and the lanthanons(III),10 the last being tetrakis anionic species. At least one example of a volatile tetrakis 0-keto-enolate salt has been reported,11 Cs[Y(CF3-COCHCOCF3)4]. The ionic charge on the 0-keto-enolate complex has been shown to produce12 a high field nuclear magnetic resonance for anions and low field shifts for cations, relative to the positions observed for the neutral species. 

Investigations into the coordination chemistry of ylides and iminophosphor-anes continue apace, an interesting development being the use of iminophos-phorane fragments as the pendant arms on new pincer ligands which help to stabilise unusual samarium and zirconium carbene complexes. 

Fiber-optic sensors, particularly fluorescent sensors, have become the object of considerable interest among researchers. The action of most fluorescent sensors is based on the change in the fluorescence properties of organic reagents immobilized on a solid matrix upon contact with solutions of metals in a continuous system. Zelters et al. [187] studied the immobilization and complex formation of immobilized Morin with zirconium and tin in order to develop a procedure for sorption fluorimetric determination of these elements. The selection of polyoxiflavones for immobilization was determined as a valuable analytical procedure. 

Interest has again continued in studies of the generation and reactivity of phosphinidene species (RP ), phosphorus analogues of carbenes, and this area has been reviewed. A review has also appeared of the use of terminal phosphinidene complexes in the formation of phosphorus-element bonds. Further studies of phosphanylidene-a -phosphoranes, RP = PR3, (regarded as phosphine-complexed phosphinidenes, i.e., ArP -PRs), have shown that the species Me3P=PAr (Ar = Mes or 2,6-Mes2C6H3) are good vehicles for the delivery of the terminal phosphinidene moiety ArP to zirconium and vanadium sites. Terminal phosphinidene complexes of cobalt, ruthenium, rhodium and osmium, and iridium, have also been... 

Biomimetic oxidations of alcohols and amines to carbonyl compounds continue to attract attention. Whilst methods are not yet of significant synthetic value, advances have been made in the development of oxidation catalysts. The isoalloxazine (1), when complexed with zirconium(iv), acts as an efficient catalyst for the oxidation of alcohols by oxygen, and the pyrimidopteridines (2) show high autorecycling efficiency in the oxidation of cyclopentanol. The deazatoxoflavin derivatives (3) oxidize primary amines to imines with high turnover of the catalyst. Subsequent hydrolysis liberates the carbonyl compound. 

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