Oximes transition metal complexes

Structural chemistrv of transition metal complexes of oximes. A. Chakravorty, Coord. Chem. Rev., 1974,13,1-46 (298). 

Hydrolysis of oximes catalyzed by transition-metal complexes has not been studied prior to a report by Kostic et al. They have reported kinetics of hydrolysis of acetoxime to acetone catalyzed by two palladium(II) complexes, identified active species in the hydrolysis reaction, proposed a reaction mechanism, and fully characterized a bis(acetoxime) complex that is relatively stable toward hydrolysis.458... 

The lithium and thallium (I) salts of i satin-3-oxime (isatin oximates) were employed in the development of ion-selective electrodes for these cations. Transition metal complexes of isatin derivatives can also be employed as catalysts for the oxidative self-coupling of alkylphenol s639,640. 

Syntheses, reactions, and biological activity of pyridine oximes 03KGS963. Transition metal complexes with 2,2 -bipyridines, pyridine-phosphines, and pyridine A-oxides as ligands 04IZV1733. 

On the other hand several transition metal complexes,e.g. dithiocarbamate and 2-hydroxylacetophenone oxime partixipate in the photostabilization of polymers (3,70-76). 

The second series of related materials was based on the (3,4-didodecyloxyphenyl)diaminodi-oxime derivative (73). Vicinal dioximes are capable of coordinating through N,N or N,0 sites of the oxime groups. Upon the complexation, the ligands fold back, and the transition metal complexes are V,V-coordinated with a square-planar structure. Both isomeric forms were selectively isolated for the nickel complexes, but only the anii-isomer for the palladium complex. The two uwti-complexes complexes exhibited a Colh phase ((73) M = Ni Cr 78 Colh H7 I M = Pd Cr 80 Colh 131 I). Most astonishing, however, was the observation of a Colh phase for the isomeric amphi-mckel complex ( , Z-isomer), between 66 °C and 145 °C. Not only was the existence of mesomorphism surprising and unexpected, but the mesophase stability also increased with respect to the anti-complex. 

The group of potential 0,N-two-center ligands includes oximes (>C=N-OH), as well as hydroxylamine NH2OH, and its derivatives. The iri -coordination of simple oximes and substituted hydroxylamines in d transition metal complexes was reported almost simultaneously in Russia [9] and elsewhere [42,43]. More speciflcally, it was found [9,44,45] that the flnal product of the reaction between tungsten (molybdenum) oxotetrafluoride and simple oximes and p-phenylhydroxylamine is a complex anion with the deprotonated organic ligand [M0F4L] (where M=Mo, W HL stands for acetoxime, acetaldoxime, benzal-doxime, 2- and 4-pyridinaldoxime, and p-phenylhydroxylamine). 

Nitroalkanes have been rarely used as substrates for catalytic reactions with carbon monoxide. This is mainly due to the fact that they usually react with transition metal complexes in their aci form [1]. Thus their reactivity is seldom comparable to the one shown by aromatic nitro derivatives. The catalytic synthesis of oximes by carbonylation of nitroalkanes is a rare example not only of their use in this type of catalysis, but also of the formation of these derivatives. 

C10H7NO2 1,2-Naphthoquinone 2-oxime (2-NiUoso-1 -naphthol) Complexing agent Extiaction-photometric Transition metals Co, Ni, Pd, Ru 3... 

Transition metal hydroxyoxime complexes have been reviewed very recently.2507 Their use in both analytical chemistry and extraction metallurgy is well known. The square planar structure of the bis chelate complex NiL (347) with the deprotonated 2-hydroxybenzaldoxime (HL) is typical of this series of nickel complexes.2508 Their bis adducts, NiLJ, with bases such as py, substituted pyridines and cyclomethyleneimines, are six-coordinate.2509 The acyl oxime (H2L) complexes are similar to the aforementioned complexes being either square planar bis chelates Ni(HL)2 (348) or octahedral bis adducts, Ni(HL)2B2.2507 When the acyl oxime acts as a dibasic ligand L, the corresponding (NiL) complexes are insoluble and involve extensive polymerization. 

A series of papers have been published on amino oxime derivatives of later transition metals, including a study of the complexes of A,A -bis[4 -benzo(15-crown-5)]diaminoglyoxime with Cu", Ni , Co", Co ", Pd", Pt and U"02. ... 

The nitrogen atom of a Schiff base or oxime can coordinate to various metal ions (alkali metal, alkaline earth metal, transition metal, heavy metal ion). In particular, chelates such as salen (bis(salicylidene)ethylenediamine), saloph (bis(salicylidene)-o-phenylenediamine), and salamo (bis(salicylideneaminooxy)ethane) afford stable metal complexes, which are utilized for a variety of molecular functions such as catalysis of organic reactions, magnetism, luminescence, etc. °... 

D-Glucosamine and either ammonia, 1,2-ethylenediamine, or 1,10-phenanthroline have been shown to form complexes with Co (III) ions, and the cobalt (ethylenediamine. D-glucosamine) complex is formed from the a-pyranose anonoo of the sugar. Aldose oximes on catalytic hydrogenation afford bis(polyhydroxyalkyl)amines. These compounds and their N-carboxymetbyl derivatives react with borate ions to give maciocyclic diborate esters which can sequester Ca, Cu and Cd ions. The coordination of some divalent transition metal imis to 2-amino-2-deoxy-D-g(ycero-D-gu/o-heptonic acid in aqueous solution has beat studied. ... 

C10H7NO2 1,2-Naphthoquinone 1-oxime (l-NiUoso-2-naphthol) Complexing agent Extiaction-photometiic Gravimetric Separation Transition and rare eartii metals Co, Fe, Mo, U Co U 3... 

Nonsteroidal antiinflammatory drugs, interaction with lithium, 36 66 No-phonon transition, 35 324 Norbomadiene complexes with cobalt, 12 286 with copper, 12 328, 330, 331 with gold, 12 348, 349 with group VIB metals, 12 231 with group VnB metals, 12 241 with iron, 12 265 with palladium, 12 314 with platinum, 12 319 with rhodium, 12 300-302 with ruthenium, 12 278, 279 with silver, 12 340-342, 344, 346 Norbomylsiloxane, 42 226, 228 Notch receptor proteins, 46 473, 475 h (N)" oxime complexes, osmium, 37 260 h (N,0) oxime complexes, osmium, 37 260 (NPr ljiFeCfrdto),], magnetization versus temperature, 43 230... 

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