Tartrate complexes

Fehlmgs solution a tartrate complex of copper(II) sulfate has also been used as a test for reducing sugars... 

Destruction of the masking ligand by chemical reaction may be possible, as in the oxidation of EDTA in acid solutions by permanganate or another strong oxidizing agent. Hydrogen peroxide and Cu(II) ion destroy the tartrate complex of aluminum. 

Copper(II) also forms stable complexes with O-donor ligands. In addition to the hexaaquo ion, the square planar /3-diketonates such as [Cu(acac)2l (which can be precipitated from aqueous solution and recrystallized from non-aqueous solvents) are well known, and tartrate complexes are used in Fehling s test (p. 1181). 

Zinc-tartrate complexes were applied for reactions of both nitrones and nitrile oxides with allyl alcohol and for both reaction types selectivities of more than 90% ee were obtained. Whereas the reactions of nitrones required a stoichiometric amount of the catalyst the nitrile oxide reactions could be performed in the presence of 20 mol% of the catalyst. This is the only example on a metal-catalyzed asymmetric 1,3-dipolar cycloaddition of nitrile oxides. It should however be no-... 

The emergence of the powerful Sharpless asymmetric epoxida-tion (SAE) reaction in the 1980s has stimulated major advances in both academic and industrial organic synthesis.14 Through the action of an enantiomerically pure titanium/tartrate complex, a myriad of achiral and chiral allylic alcohols can be epoxidized with exceptional stereoselectivities (see Chapter 19 for a more detailed discussion). Interest in the SAE as a tool for industrial organic synthesis grew substantially after Sharpless et al. discovered that the asymmetric epoxidation process can be conducted with catalytic amounts of the enantiomerically pure titanium/tartrate complex simply by adding molecular sieves to the epoxidation reaction mix-... 

Figure 6.1 Proposed structure for the titanium tartrate complex (1) and its transformation after addition of reagents (e. g., TBHP and olefin), forming (+)-2.

Reduction of CIOJ by citrate, tartrate and EDTA complexes of Fe(II) and by Cu(NH3)4 has been examined polarographically. All four reactions are first-order in reductant and C102. The data for the citrate and tartrate complexes were not reproducible but estimates of k2 (27 °C) were obtained. The rate data are... 

The original titanium-mediated epoxidation is a stoichiometric reaction.27 However, the epoxidation can be carried out with a catalytic amount (5-10 mol.%) of titanium-tartrate complex in the presence of molecular sieves.29 The advantages of the catalytic procedure are ease of product isolation, increased yield, economy, and a high substrate concentration. 

Solid-state structures of two bismuth tartrate complexes reveal a similar asymmetric unit composed of two tartrate ligands on a bismuth center and are distinguished by replacement of a proton in Bi(H3tar)(H2tar) 3H20 (160) with by an ammomium ion in NH4[Bi (H2tar)2(H20)] H20 (161). The nine-coordinate bismuth environments in each structure are very similar, as illustrated in 48, respectively,... 

Figure 5.46 Schematic representation of helical and twisted ribbons as discussed in Ref. 165. Top Platelet or flat ribbon. Helical ribbons (helix A), precursors of tubules, feature inner and outer faces. Twisted ribbons (helix B), formed by some gemini surfactant tartrate complexes, have equally curved faces and C2 symmetry axis. Bottom Consequences of cylindrical and saddlelike curvatures in multilayered structures. In stack of cylindrical sheets, contact area from one layer to next varies. This is not the case for saddlelike curvature, which is thus favored when the layers are coordinated. Reprinted with permission from Ref. 165. Copyright 1999 by Macmillan Magazines.

There are several Ti-tartrate complexes present in the reaction system. It is believed that the species containing equal moles of Ti and tartrate is the most active catalyst. It promotes the reaction much faster than Ti(IV) tetraalkoxide alone and exhibits selective ligand-accelerated reaction.9... 

A major advantage that nonenzymic chiral catalysts might have over enzymes, then, is their potential ability to accept substrates of different structures by contrast, an enzyme will select only its substrate from a mixture. Striking examples are the chiral phosphine-rhodium catalysts, which catalyze die hydrogenation of double bonds to produce chiral amino acids (10-12), and the titanium isopropoxide-tartrate complex of Sharpless (11,13,14), which catalyzes the epoxidation of numerous allylic alcohols. Since the enantiomeric purities of the products from these reactions are exceedingly high (>90%), we might conclude... 

Interaction Between Partial Reactions. The original mixed-p)otential theory assumes that the two partial reactions are independent of each other (1). In some cases this is a valid assumption, as was shown earlier in this chapter. However, it was shown later that the partial reactions are not always independent of each other. For example, Schoenberg (13) has shown that the methylene glycol anion (the formaldehyde in an alkaline solution), the reducing agent in electroless copper deposition, enters the first coordination sphere of the copper tartrate complex and thus influences the rate of the cathodic partial reaction. Ohno and Haruyama (37) showed the presence of interference in partial reactions for electroless deposition of Cu, Co, and Ni in terms of current-potential curves. 

Geminal dibromocyclopropanes have been reduced by chromium(lI) - (-i-)-tartrate complex and by butyllithium - (+)-sparteine complex to give cyclic allenes and 1-phenyl-l,2-butadiene with very low enantioselectivity (< 1 % op)122. In addition, cyclic diallenes of unknown optical purity have been reported123, l24, e.g., 3,4,9,10-cyclododecatetraene-l,7-dione is prepared using a stoichiometric amount of methyllithium and a sixfold excess of (-)-sparteine123,124. 

A,A-Dimethylselenourea was used with ammonia baths and additional citrate or tartrate complexation at pH of 11.3 (citrate bath) or 10.4 (tartrate) to deposit CdSe on glass at room temperature [97]. No XRD of the films was detected. From the... 

Only one group has reported CD of SbiSes. The solution used was potassium an-timonyl tartrate, complexed with triethanolamine and ammonia. Selenosulphate was used as the Se source. No XRD pattern was found, as for the sulphide deposited under equivalent conditions. The bandgap was 1.88 eV, and resistivity O-cm [13,14]. Continued study of this deposition showed the effect of various parameters on deposition rate and film thickness (the latter typically reaching 1 p.m) [15]. This study also described some photoelectrochemical behavior of these films (Chap. 9). 

Figure 27 Schematic representation of [(VOJ tartiJ4 units in tartrate complexes. Internuclear distances are given for (a) (NH4)4[(V0)2 (+)-tart 2]-H206flf and (b) Na4[(V0)2 (+)-tart (-)-tart ]-12H20616...

Auxiliary complexing agents such as NH3, tartrate, citrate, or triethanolamine may be employed to prevent metal ion from precipitating in the absence of EDTA. For example, Pb2+ is titrated in NH, buffer at pH 10 in the presence of tartrate, which complexes Pb2+ and does not allow Pb(OH)2 to precipitate. The lead-tartrate complex must be less stable than the lead-EDTA complex, or the titration would not be feasible. 

Sachtler proposes a "dual site" mechanism where the hydrogen is dissociated on the Ni surface and then migrates to the substrate which is coordinated to the adsorbed nickel-tartrate complex. In this context it is of interest that the well known Sharpless epoxidation probably takes place on a dimeric tartrate complex of Ti. Sachtler suggests that both the anion and the cation have a function which varies according to the conditions used. It is not clear whether the spillover mechanism is also proposed for the reaction in solution [55]. 

An important improvement in the asymmetric epoxidation process is the finding, reported in 1986, that by adding molecular sieves to the reaction medium virtually all reactions can be performed with a catalytic amount (5-10 mol %) of the Ti-tartrate complex [3]. Previously, only a few structural classes of allylic alcohols were efficiently epoxidized by less than stoichiometric amounts of the complex, and most reactions were routinely performed with stoichiometric quantities of the reagent. 

This section presents a summary of the currently preferred conditions for performing Ti-catalyzed asymmetric epoxidations and is derived primarily from the detailed account of Gao et al. [4]. We wish to draw the reader s attention to several aspects of the terminology used here and throughout this chapter. The terms Ti-tartrate complex and Ti-tartrate catalyst are used interchangeably. The term stoichiometric reaction refers to the use of the Ti-tartrate complex in a stoichiometric ratio (100 mol %) relative to the substrate (allylic alcohol). The term catalytic reaction (or quantity) refers to the use of the Ti-tartrate complex in a catalytic ratio (usually 5-10 mol %) relative to the substrate,... 

---