Ligands, carboxylated

In titanium acylates, the carboxylate ligands are unidentate, not bidentate, as shown by ir studies (333,334). The ligands are generally prepared from the hahde and silver acylate (335). The ben2oate is available also from a curious oxidative addition with ben2oyl peroxide (335—338) ... 

Zirconium oxalates exist as compounds, double compounds, and mixed oxalato complexes (165,195,225—226). When the carboxylate ligand is a longer alkyl chain, the materials often are called zirconium soaps. 

On the other hand, Doyle et al. have developed methyl 2-oxoimidazolidine-4(carboxylate ligands, containing 2-phenylcyclopropane attached at the 1-iV-acyl site, such as the (4(5),2 (7 ),3 (7 )-HMCPIM) ligand. The resulting dirhodium complex led, for the cyclopropanation of styrene with EDA, to the corresponding cyclopropane with 68% ee and 59% yield, but with almost... 

Fig. 4. Proposed catalytic cycle for the hydroxylation of methane by MMO. The reductase and B components may interact with the hydroxylase in one or more steps of the cycle. Protons are shown in the step in which intermediate Q is generated, but other possibilities exist (see Fig. 3 and the text). The curved line represents a bridging glutamate carboxylate ligand.

NMR measurements also provide information on the coordination of the ligands in the uranyl polymers. Solid-state I c-NMR confirms the coordination modes of the carboxylate ligands to the uranyl ion that is, both monodentate and bidentate carboxylate coordination modes are evident. The uranyl dicarboxyl ate polymers which possess two moles of coordinated DMSO exhibit two carbon-13 carbonyl resonances, one at about 175 ppm downfield from tetramethylsilane (TMS) and one at about 185 ppm. The polymers which possess only one mole of coordinated DMSO exhibit only the carbonyl peak near 185 ppm. Based on other known coordination compounds, the 175 ppm peak can be assigned to monodentate carboxylate and the 185 ppm peak to bidentate carboxylate. Thus, 7-coordination predominates in the polymers with either one or two moles of solvent coordinated to the uranyl ion, which is consistent with the infrared results reported elsewhere (5). 

The "unfolded-drum" or "ladder" compound 2 has crystallographic symmetry. This corresponds to the idealized molecular symmetry and, therefore, there are three chemically inequivalent types of Sn atoms in the molecule, although all are hexacoordinated. The oxygen atoms in the open form can be subdivided into two types, as in the case of the drum molecule tricoordinate framework oxygen atoms and the dicoordinate oxygen atoms of the bridging carboxylate ligands. 

Metalloenzymes with non-heme di-iron centers in which the two irons are bridged by an oxide (or a hydroxide) and carboxylate ligands (glutamate or aspartate) constitute an important class of enzymes. Two of these enzymes, methane monooxygenase (MMO) and ribonucleotide reductase (RNR) have very similar di-iron active sites, located in the subunits MMOH and R2 respectively. Despite their structural similarity, these metal centers catalyze very different chemical reactions. We have studied the enzymatic mechanisms of these enzymes to understand what determines their catalytic activity [24, 25, 39-41]. 

The active-site model (and the ONIOM model system) includes Fe, one aspartate and two histidine ligands, a water ligand and selected parts of the substrate (see Figure 2-6). The 2-histidine-1-carboxylate ligand theme is shared by several other non-heme iron enzymes [59], For the protein system, we used two different... 

Acetate remains the classical carboxylate ligand, with the capacity to bind in monodentate bidentate chelate (/i2), or bridging modes. Whereas early chemistry featured simple fii... 

Multinuclear mixed-metal complexes can be formed with carboxylate ligands. 

L-piperidine-2-carboxylic acid is a non-proteinogenic amino acid that is a metabolite of lysine. The zinc complexes of DL-piperidine-2-carboxylic acid, DL-piperidine-3-carboxylic acid, and piperidine-4-carboxylic acid have been studied. The X-ray crystal structures have been determined for the latter two. [ZnCl2(DL-piperidine 3-carboxylate)2] (42) is monomeric with a tetrahedral metal center and monodentate carboxylates. [Zn2Cl4(piperidine-4-carboxylate)2] (43) contains two bridging carboxylates in a dimeric structure. IR studies suggest that the DL-piperidine-2-carboxy-lato zinc has monodentate carboxylate ligands coordinating.392... 

Scheme 4. Exchange of carboxylate ligands in dizinc complexes 49a-f. The bowl-shaped representation of the host molecules should not be confused with the one used for the cyclodextrins.

It has already been mentioned that utilization of the permethylated ligand (L19)2 in place of (L23)2 drastically alters the ease of substitution reactions of the [M2(L19)(C1)]+ complexes (Section III.D). Further studies revealed a remarkable influence of the hydrophobic pocket on the rate and course of several substrate transformations, as for instance the fixation of carbon dioxide (239) (Scheme 8), the cis-bromination of a,/)-unsaturated carboxylate ligands (256), and some Diels-Alder reactions (215). Of these the latter two reactions will now be discussed. 

The use of a metalated container in stereoselective transformations has only recently begun to be explored (284). This prompted us to study the bromination of the a,/J-unsaturated carboxylate ligands in dicobalt(III) complexes of the type [Co2(Ll9)( -02CCH = CHR)]3+ (256). 

The observation that a,/ -unsaturated carboxylate ligands can be readily accommodated in the binding pocket led us to study an orienting reaction between the dinickel complex 101 and 2,3-dimethylbutadiene (Scheme 10). However, the reaction did not proceed, even when the reaction mixture was heated at 210°C for 24 h. The inhibition of the Diels-Alder reaction can be traced to the limited space in the binding pocket of 101. 

A review is concerned with carboxylate complexes of platinum metals and their versatility as catalysts their moderate stability and high lability (the monodentate, bidentate character of the carboxylate ligand, and its ready removal by acid) render them particularly promising (157). 

A greater tendency of rhenium complexes (compared to technetium analogues) to expand their coordination numbers has been invoked to rationalize the stronger interaction of the perrhenate ion with carboxylate ligands. This association has been suggested as a possible cause of the different quantitative biodistribution and excretion characteristics of pertechnetate and perrhenate perrhenate is accumulated in thyroid to a lesser extent and renally excreted more rapidly than pertechnetate [6]. 

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