Principles of Mononucleating and Binucleating Ligand Design

Gavrilova, Anna L.; Bosnich, B.

doi:10.1002/chin.200419290

Cited by 15 publications

(20 citation statements)

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“…Some of the best known examples are the cofacial diporphyrins, which are capable of catalyzing multielectron redox processes [22][23][24] . Several research groups have prepared complexes from dipyridyltriazoles (though they lead to relatively short metal-metal distances) 25 ; other binucleating ligands have also been employed 26 . We report herein a binuclear metallacyclic copper complex that can selectively capture CO 2 from air and reduce it to oxalate, in the form of an oxalate-bridged complex.…”

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confidence: 99%

RETRACTED ARTICLE: Reduction of carbon dioxide to oxalate by a binuclear copper complex

2014

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confidence: 99%

RETRACTED ARTICLE: Reduction of carbon dioxide to oxalate by a binuclear copper complex

2014

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“…The design of multidentate ligands and their metallosupramolecular chemistry are of great interest in the last few years [1][2][3]. The condensation reaction of an aromatic carbaldehyde with a primary amine has been shown to offer an easy and inexpensive way of forming a variety of polydentate Schiff base ligands.…”

Section: Discussionmentioning

confidence: 99%

Crystal structure of bis(4-chloro-2-((3-dimethylaminopropylimino)- methyl)phenolato)thiocyanato-cobalt(III) perchlorate hemihydrate, [Co(C12H16ClN2O)(C12H17ClN2O)(NCS)][ClO4] · 0.5H2O

Wang¹,

Li²

2007

Zeitschrift Für Kristallographie - New Crystal Structures

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Source of materialReagents and solvents used were of commercially available quality. 5-Chlorosalicylaldehyde (0.2 mmol, 31.5 mg) and N,N-dimethylpropane-1,3-diamine (0.2 mmol, 20.4 mg) were dissolved in a methanol solution (20 ml). The mixture was stirred for 30 min at room temperature. To the above solution was added with stirring an aqueous solution (5 ml) of cobalt(III) perchlorate hexahydrate (0.1 mmol, 46.5 mg). The final mixture was stirred at room temperature for another 30 min and filtered. Red block-shaped crystals, suitable for X-ray structure determination were formed by slow evaporation of the solvent from the filtrate for a week. Elemental analysis found: C, 42.27 %; H, 5.02 %; N, 9.80 %; calc. for C 25H34Cl3CoN5O6.5S: C, 42.54 %; H, 4.85 %; N, 9.92 %. Experimental detailsAll H atoms were positioned geometrically and constrained as riding atoms, with CH distances of 0.93 Å 0.97 Å, NH distance of 0.91 Å, and U iso (H) set to 1.2U eq (C/N) and 1.5U eq (methyl C) of the parent atoms. The O atoms of the perchlorate anion are disordered over two distinct sites with occupancies of 0.399/ 0.601(8). The ClO and O···O distances in both disordered components were restrained to be equal. The occupancy of the water O7 atom was initially refined and finally restrained to 0.5, which is proved by the elemental analysis. The large R values are mainly caused by the disorder of the perchlorate anion and the lattice water molecule. DiscussionThe design of multidentate ligands and their metallosupramolecular chemistry are of great interest in the last few years [1-3]. The condensation reaction of an aromatic carbaldehyde with a primary amine has been shown to offer an easy and inexpensive way of forming a variety of polydentate Schiff base ligands. It has previously been shown that such ligands readily lead to the formation of diverse complexes [4][5][6][7]. The title crystal structure consists of a mononuclear Schiff base cobalt(III) cationic complex moiety, a disordered perchlorate anion and half a lattice water molecule. The Co atom in the complex is six-coordinated by two Schiff base ligands and one terminal thiocyanate anion, forming an octahedral environment. One of the Schiff base ligands coordinates to the Co atom through the NNO donor set, while the other one coordinates to the metal atom through the phenolate O and imine N atoms, with the amine N atom protonated and not coordinated to the metal center. The thiocyanate anion acts as a monodentate ligand and ligates to the metal through the terminal N atom. All the bond lengths and angles subtended at the metal center are typical and comparable to those observed in other cobalt(III) complexes [8][9][10][11][12]. The dihedral angle between the two benzene rings is 31.0(7)°. The chelate ring formed by the atoms Co1, N1, C8, C9, C10, and N2 in the complex has a chair conformation. The diagonally positioned atoms, Co1 and C9, are shifted from the least-squares plane defined by the atoms N1, N2, C8, and C10 by 1.015(5) Å and 0.69(1) Å, respectively.

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“…Because some of the known enzymes have homobimetallic structures, dinuclear metal complexes such as dinuclear copper, dinuclear iron, dinuclear manganese and dinuclear nickel etc. [78] have been investigated in catalytic reactions [70]. According to their structures and the way they interact with reagents and substrates, dinuclear catalysts can be roughly classified into two types.…”

Section: Homobimetallic Catalysis For Organic Synthesismentioning

confidence: 99%

“…Maggini reviewed P,N-binucleating ligands in bimetallic complexes [80], Peris et al [81] reviewed complexes with (N-heterocyclic carbene) ligands while Gavrilova and Bosnich [78] established the principles of ligand design.…”

Section: Homobimetallic Catalysis For Organic Synthesismentioning

confidence: 99%

Recent developments in homobimetallic reagents and catalysts for organic synthesis

Shimeng

et al. 2011

Chin. Sci. Bull.

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Organometallics are a family of useful organic chemicals because they play important roles in organic synthesis as reagents and as catalysts. They can be classified according to the number of metals they contain. Bimetallic compounds are important organometallics and they are either homobimetallic or heterobimetallic depending on whether the two metals are the same or different. In this paper, we focus on homobimetallic compounds. Homobimetallic compounds are generally used as dianions to react with electrophiles in organic synthesis. Recently, homobimetallics have also been used as catalysts in organic reactions such as in asymmetric reactions. homobimetallics, reagent, catalyst, synthesis, application Citation:Wu W, Gu D L, Wang S M, et al. Recent developments in homobimetallic reagents and catalysts for organic synthesis.

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Principles of Mononucleating and Binucleating Ligand Design

Abstract: For Abstract see ChemInform Abstract in Full Text.

Cited by 15 publications

References 1 publication

RETRACTED ARTICLE: Reduction of carbon dioxide to oxalate by a binuclear copper complex

RETRACTED ARTICLE: Reduction of carbon dioxide to oxalate by a binuclear copper complex

Crystal structure of bis(4-chloro-2-((3-dimethylaminopropylimino)- methyl)phenolato)thiocyanato-cobalt(III) perchlorate hemihydrate, [Co(C12H16ClN2O)(C12H17ClN2O)(NCS)][ClO4] · 0.5H2O

Recent developments in homobimetallic reagents and catalysts for organic synthesis

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