Oxime and oximate metal complexes: unconventional synthesis and reactivity

Kukushkin, Vadim Yu.; Pombeiro, Armando J. L.

doi:10.1016/s0010-8545(98)00215-x

Cited by 259 publications

(96 citation statements)

References 83 publications

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“…Introduced first in 1905 by Tschugaeff [12], dimethylglyoxime as a reagent for nickel, the oximes as potential ligands have been increasingly expanding its horizon in coordination chemistry. Structure, stability and reactivity of molecules, biochemical models, analytical and organometallic chemistry and particularly syntheses of molecules with unusual electronic properties are the aspects that kindled the interest for the oxime-based ligands [13][14][15][16][17]. Due to the marked ability to form bridges with metal ions, oxime ligands may be used to obtain polynuclear compounds with molecular magnetism and supramolecular structure [18,19].…”

Section: Introductionmentioning

confidence: 99%

Synthesis, crystal structures, hydrogen bonding graph-sets and theoretical studies of nickel (+II) co-ordinations with pyridine-2,6-dicarboxamide oxime

Hamdaoui

Messai

Benyza

et al. 2017

J. Fundam and Appl Sci.

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Section: Introductionmentioning

confidence: 99%

Synthesis, crystal structures, hydrogen bonding graph-sets and theoretical studies of nickel (+II) co-ordinations with pyridine-2,6-dicarboxamide oxime

Hamdaoui

Messai

Benyza

et al. 2017

J. Fundam and Appl Sci.

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“…Some metal oximates have been reported and structurally characterized. [21,27] The structure of 3 retains an Al 2 N 2 core as in 1, the Al(1A)-N(2)-Al (1) and N(2A)-Al(1)-N(2) angles being 91.7(1)8 and 88.3(1)8, respectively. The aluminum centers have tetrahedral geometries with the oximate fragments (O À N=CMe 2 ) bound to the aluminum centers in a h 2 -fashion through the N and O atoms.…”

Section: Resultsmentioning

confidence: 98%

Aluminum Compounds Containing η¹‐ and/or η⁵‐Bidentate Dianionic Pyrrolyl–Methylamide Ligands

Chen

Lin

Chun-yin

et al. 2008

Chemistry A European J

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A series of dialuminum compounds have been synthesized and their reactivity and application for lactide polymerization have been studied. The reaction of AlH3 x NMe3 with [C4H3NH(2-CH2NHtBu)] in diethyl ether generated a dimeric aluminum hydride compound, [[[C4H3N(2-CH2NtBu)]AlH]2] (1). The structure of 1 was confirmed by spectroscopy of a deuterated analogue of 1 with an Al--D function. Direct treatment of [C4H3NH(2-CH2NHtBu)] with LiAlH4 in diethyl ether resulted in colorless crystals of [[Li[micro-eta1:eta5-C4H3N(2-CH2NtBu)]2Al]2] (2) in 80 % yield after recrystallization from a toluene solution. The micro-eta1:eta5-pyrrolyl protons exhibit high-field shifts at delta=5.73, 6.15, and 6.72 comparable to a similar eta5-bonding mode in the literature. Treatment of 1 with 1 equiv acetone oxime or acetone in dichloromethane gave [[[C4H3N(2-CH2NtBu)]Al[varkappaO,varkappaN-(ON==CMe2)]]2] (3) and [[[C4H3N(2-CH2NtBu)]Al(O--CHMe2)]2] (4) in 67 % and 60 % yield, respectively. Compounds 1-4 have been characterized by X-ray diffractometry and were used as catalysts for epsilon-caprolactone polymerization.

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“…Although the primary attention on them was devoted to preparative routes of coordination compounds and to analytical chemistry purposes, their metal-mediated reactions and high-nuclearity, exchange-coupled metal clusters have caught the eyes of different research teams in the last two decades. 2,3 Restricting ourselves to the field of molecular magnetism, the oxime group, >C=NOH, has two characteristics that make it very appealing: (i) its ability to act as a bridge between two different metal ions after deprotonation, to afford a great variety of heterobimetallic compounds, [M-(m-NO oximato )-M'], and (ii) its remarkable capability to mediate very strong magnetic interactions between the spin carriers bridged by the double NO oximato pathway. As illustrative examples of the great efficiency of this exchange pathway to mediate electronic interactions, one can cite the practically diamagnetic character at room temperature of a family of bis(oximato)-bridged binuclear copper(II) complexes with an intramolecular copper-copper separation of ca.…”

Section: Introductionmentioning

confidence: 99%

“…The use of a complex as ligand allowed us to achieve this goal, the starting building block being the species shown in Scheme 2. Their reaction with manganese(II) acetate in methanol in air afforded the compounds of formula [MnCu(deg) 2 …”

Section: Introductionmentioning

confidence: 99%

Slow relaxation of the magnetization in Oximato-bridged heterobimetallic Copper(II)-Manganese(III) chains

Ruiz

Castro

Pardo

et al. 2011

J. Braz. Chem. Soc.

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(3), com oxidação do íon manganês(II) a manganês(III) na presença de ar. Na ausência de monocristais para análise por difratometria de raios X, técnicas de absorção de raios X (EXAFS e XANES) foram usadas a 40 K para caracterização estrutural de 1-3. A análise dos dados de absorção de raios X revelou que 1-3 apresentam cadeias bimetálicas de íons Cu II e Mn III ligados por pontes oximato, em ambiente octaédrico (CuN 4 O 2 e MnO 6 ) alongado. Os estudos de propriedades magnéticas de 1-3 revelaram um comportamento metamagnético devido à coexistência de acoplamentos ferromagnéticos intracadeias fortes [J = +52.5 (1), +49.1 (2) e +52.1 cm -1 (3)] e interações antiferromagnéticas intercadeias fracas [j = −0.070 (1), −0.075 (2) e −0.078 cm -1 (3)]. A ortogonalidade estrita entre o orbital magnético do cobre(II) e aquele do centro magnético de manganês(III), junto com a conhecida habilidade do grupo oximato em mediar interações magnéticas quando atua como ponte entre dois íons metálicos, é responsável pela forte interação ferromagnética intracadeia em 1-3. Medidas de susceptibilidade sob corrente alternada realizadas para 1-3 em temperatura baixa e sob campo magnético dc igual a zero revelaram uma dependência do sinal ac fora de fase com a frequência do campo oscilante, como esperado para magnetos do tipo single-chain.The use of the oximato-containing copper(II) complexes, [Cu(Hdeg) (3) where the starting manganese(II) ion was oxidized to manganese(III) by air. In the lack of single crystals suitable for X-ray diffraction analysis, X-ray absorption techniques (EXAFS and XANES) at 40 K were used for the structural characterization of 1-3. The analysis of the X-ray absorption data reveals that 1-3 are oximato-bridged Cu II -Mn III bimetallic chains with elongated octahedral CuN 4 O 2 and MnO 6 surroundings. The study of the magnetic properties of 1-3 reveals a metamagnetic-like behavior due to the coexistence of strong intrachain ferromagnetic couplings [J = +52.5 (1), +49.1 (2) and +52.1 cm -1 (3)] and weak interchain antiferromagnetic interactions [j = −0.070 (1), −0.075 (2) and −0.078 cm -1 (3)]. The strict orthogonality between the magnetic orbital of the copper(II) ion and those of the manganese(III) center, together with the well known ability of the oximato group to mediate magnetic interactions when acting as a bridge between two metal ions, account for the relatively strong intrachain ferromagnetic coupling in 1-3. Alternating current susceptibility measurements for 1-3 in the low temperature range under zero dc magnetic field reveal a frequency-dependence of the out-of-phase ac signal as expected for single chain magnets.Keywords: metal oximates, heterobimetallic complexes, complex as ligand strategy, exchange coupling, single chain magnets Ruiz et al. 977 Vol. 22, No. 5, 2011 IntroductionSince the first report concerning the use of the dimethylglyoxime (H 2 dmg) as a reagent for nickel(II), 1 oximes as ligands have been widely used in coordination chemistry. Although the primary attention on them wa...

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Oxime and oximate metal complexes: unconventional synthesis and reactivity

Cited by 259 publications

References 83 publications

Synthesis, crystal structures, hydrogen bonding graph-sets and theoretical studies of nickel (+II) co-ordinations with pyridine-2,6-dicarboxamide oxime

Synthesis, crystal structures, hydrogen bonding graph-sets and theoretical studies of nickel (+II) co-ordinations with pyridine-2,6-dicarboxamide oxime

Aluminum Compounds Containing η¹‐ and/or η⁵‐Bidentate Dianionic Pyrrolyl–Methylamide Ligands

Slow relaxation of the magnetization in Oximato-bridged heterobimetallic Copper(II)-Manganese(III) chains

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Oxime and oximate metal complexes: unconventional synthesis and reactivity

Cited by 259 publications

References 83 publications

Synthesis, crystal structures, hydrogen bonding graph-sets and theoretical studies of nickel (+II) co-ordinations with pyridine-2,6-dicarboxamide oxime

Synthesis, crystal structures, hydrogen bonding graph-sets and theoretical studies of nickel (+II) co-ordinations with pyridine-2,6-dicarboxamide oxime

Aluminum Compounds Containing η1‐ and/or η5‐Bidentate Dianionic Pyrrolyl–Methylamide Ligands

Slow relaxation of the magnetization in Oximato-bridged heterobimetallic Copper(II)-Manganese(III) chains

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Aluminum Compounds Containing η¹‐ and/or η⁵‐Bidentate Dianionic Pyrrolyl–Methylamide Ligands