Nitrogen coordination

Experimental confirmation of the metal-nitrogen coordination of thiazole complexes was recently given by Pannell et al. (472), who studied the Cr(0), Mo(0), and W(0) pentacarbonyl complexes of thiazole (Th)M(CO)5. The infrared spectra are quite similar to those of the pyridine analogs the H-NMR resonance associated with 2- and 4-protons are sharper and possess fine structure, in contrast to the broad, featureless resonances of free thiazole ligands. This is expected since removal of electron density from nitrogen upon coordination reduces the N quad-rupole coupling constant that is responsible for the line broadening of the a protons. 

The physical properties of commercial alkoxysilanes are provided in Table 1. Two classes of silane esters have very distinct properties and are generally considered apart from alkoxysilanes. Sdatranes are compounds derived from trialkanolamines and have siHcon—nitrogen coordination. These are generally hydrolytically stable and have unique physiological properties (3). A second special class of monomeric esters are cycHc diesters of polyethyleneoxide glycols designated sila-crowns, which have appHcation as catalysts (4). Neither silatranes nor sila-crowns are considered herein. 

The most common catalysts for ATRP are complexes based on a copper(T) halide and nitrogen based ligand(s). Various ligands have been employed and those most frequently encountered are summarized in Table 9.5. Typically, four nitrogens coordinate to copper. The bidentate bipyridyl (bpy) ligands 132-133 are known to form a 2 1 complex. The tetradentate ligands are expected to form a 1 1 complex. 

Nitrogen coordination of the Rieske cluster had been suggested by Blumberg and Peisach (4) as early as 1974. However, it was only after the pioneering Mossbauer studies of Fee et al. (5) that the coordina-... 

Associated to copper(II) pre-catalysts, bis(oxazolines) also allowed the asymmetric Diels-Alder and hetero Diels-Alder transformations to be achieved in nearly quantitative yield and high diastereo- and enantioselectivities. Optically active sulfoximines, with their nitrogen-coordinating site located at close proximity to the stereogenic sulfur atom, have also proven their efficiency as copper ligands for these asymmetric cycloadditions. Other precursors for this Lewis acid-catalyzed transformation have been described (e.g., zinc salts, ruthenium derivatives, or rare earth complexes) which, when associated to bis(oxazolines), pyridine-oxazolines or pyridine-bis(oxazolines), led to efficient catalysts. 

Thiourea Ugands can be bounded to the metal centre through one nitrogen atom, the sulfur atom, or the C = S double bond. These coordination modes were studied by density functional theory calculations for Rh-thiourea complexes (Scheme 13). No stable structure was attained by optimisation of the nitrogen coordination mode I but optimised geometries as trigonal-bipyramidal complexes were obtained for modes II and III. An coordination is determined for the latter complex through both S and C atoms. As this... 

Almost any class of reduced nitrogen compound can serve as the nitrosatable precursor of an N-nitroso compound. To make matters worse, every nitrogen coordination state from primary to quaternary has been converted to a nitrosamine. A glance at the list of some of the known nitrosatable substrates given in Table II illustrates what a wide variety of N-nitroso compounds analysts might expect to encounter in our complex environment. 

When 4, 4 -dimethyl-2 -(2-thienyl)-2 -oxazoline lithiated at is reacted with [Au (C6F5)(tht)] the neutral nitrogen-coordinated pentafluorophenylgold complex and not the expected monocarbene complex [68] is obtained. 4-Methylthiazole, 4-methyl-2-mehylsulfanylthiazole and piperidine react with [Au(C6F5)(tht)] forming the complexes shown in Figure 3.4 [73]. 

Metal-Nitrogen Bond Lengths and Torsion Angles between the Metal and Nitrogen Coordination Planes for Three-Coordinate Aluminum, Gallium, Indium, and Thallium Amides... 

Therefore, sulfur coordination of NCS ligand to ruthenium shows a carbon resonance at around 120-125 ppm, compared to the nitrogen coordination of NCS ligand, where the 13C resonance is in the region of 130-145 ppm.46... 

The geometry about a ligand nitrogen coordinated to a metal ion is assumed to be planar with bond directions defined in Fig. 28. The hybridizations of the nitrogen orbitals for different angles between the bonds in the plane can be written as ... 

Complexes of picolinamide with lanthanide perchlorates, nitrates, and isothiocyanates have been isolated by Condorelli et al. (59). All these complexes show changes in the stoichiometry on going from La(III) to Lu(III). The ligand acts as bi-dentate with the oxygen of the amide group as well as the heterocyclic nitrogen coordinating to the metal (Structure I). While the anions in the perchlorate complexes are not coordinated to lanthanide ions, those in the nitrate and isothiocyanate complexes are coordinated. 

Lithiation of the conformationally constrained ferrocenyloxazoline 308 (Scheme 142) provided useful information about the mechanism by which lithiation of 305 achieves diastereoselectivity . The product 310 must have arisen from an organolithium 309 in which the oxazoline nitrogen coordinates to the hthium (Scheme 142). It is likely that... 

Mixed crystals of type II have been used in the form of thin films on electrodes as well as in the form of chemically synthesized powders immobilized on electrodes. Depending on the radii of the ions involved in the synthesis, solid solutions can also be formed as single phases. In the case of K CuCo[Fe(CN)(5] films, XRD results indicated that a single phase with a cubic face-centered symmetry was formed [31]. The situation is more complex in the case of K NiPd[Fe(CN)6] deposited as a thin film on electrodes [32]. Kulesza etal. have pointed out that there is a critical concentration of Pd + below which Pd + was taken as the countercation at interstitial position, while above that value a solid solution is formed in which both Ni " " and Pd + are nitrogen coordinated. 

Fig. 4 Correlation between the formal potentials of the hexacyanoferrate units of the solid hexacyanoferrates and the ion potential (charge/radius) of the nitrogen coordinated metal ions [53, 55].

The formal potentials of solid hexa-cyanometalates can also be correlated with the lattice constants, that is, with a parameter that depends mainly on the radii of the two metal ions forming the framework of the compounds. This theoretically derived dependence can be verified when the nitrogen coordinated metal ion and the inserting metal ions are kept constant and the carbon coordinated metal ions are varied, for example, when hexacyanoferrate, hexa-cyanocobaltate, hexacyanomanganate, and so on are compared [53, 55]. The equation... 

A comparison with the glycine work suggests that it is the nitrogen coordination rather than the carboxylate coordination which accelerates the water substitution of the metal complex. It appears that three nitrogens coordinated to Ni(II) gives a labile system which is diminished by having four or five nitrogens coordinated. 

As shown in Fig. 2.5, the cyclic voltammograms for Prussian blue attached to paraffin-impregnated graphite electrodes (PIGEs) in contact with aqueous electrolytes exhibit two well-defined one-electron couples. Prussian blue crystals possess a cubic structure, with carbon-coordinated Fe + ions and nitrogen-coordinated Fe + ions, in which potassium ions, and eventually some Fe + ions, are placed in the holes of the cubes as interstitial ions. The redox couple at more positive potentials can be described as a solid-state process involving the oxidation of Fe + ions. Charge conservation requires the parallel expulsion of K+ ions [77] ... 

FIGURE 85. Schematic structures of zinc enolates stabilized by intramolecular nitrogen coordination... 

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