Structural Characterization of Encapsulation Reactions Based on the Tris(ethane-1,2-diamine)cobalt(III) Ion

Clark, IJ; Geue, RJ; Engelhardt, Lutz M.; Harrowfield, JM; Sargeson, A. M.; White, AH

doi:10.1071/ch9931485

Cited by 25 publications

(17 citation statements)

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“…The nitro-cap is apparent in Figure 5. Structurally characterised Co III complexes from the sar family abound in the literature, 1,25,26 and most exhibit the same lel3 conformation seen here (with the -CH2-CH2groups of all five-membered chelate rings aligned with the 3-fold axis of the complex.…”

Section: Resultssupporting

confidence: 70%

A Functionalised Macrobicycle Complex Available for Surface Immobilisation and Protein Grafting

Bernhardt¹,

Harrowfield²,

Kim

et al. 2007

Bulletin of the Korean Chemical Society

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The conversion of both the racemic and resolved forms of the Co(III) complex of an hydroxymethyl-substituted tripodal hexamine to macrobicycles via reaction with formaldehyde and nitromethane (and subsequent reduction of the product) has been conducted. The prospect is that it will provide cage complexes in which the hydroxyl substituent is sufficiently remote from the metal ion centre for its nucelophilicity to be largely unaffected. X-ray structure determinations have been used to characterise these new cage species as well as some complexes of the precursor hexamine and its mono-aminal. The electrochemistry and optical activity of the complexes have also been studied in detail.

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Section: Resultssupporting

confidence: 70%

A Functionalised Macrobicycle Complex Available for Surface Immobilisation and Protein Grafting

Bernhardt¹,

Harrowfield²,

Kim

et al. 2007

Bulletin of the Korean Chemical Society

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“…The Co-N and Co-0 distances lie within the range seen in many related c o m p l e x e ~, ~~~~~ (although significant variations are found, notably in situations such as that offered by complex 7, where a deprotonated hydroxyl ligand is present) and some distortions of the coordination sphere from true octahedral geometry are expected given the asymmetric ligand environment. Five-membered chelate ring donor atom-Co-donor atom bond angles for the octahedral face spanned by the 1 -aminofructosylamine moiety are small but a similar contraction has been observed in thecagecompiex [CoL][NO,], (L = 1 -chloro-8-chloromethyl-3,6,10,13,16, 19-hexaazabicyclo[6.6.5]nonadecane), 29 where an octahedral face spanned by a similar chelate ring structure is present. Geometry within the sugar pyranose rings is similar to that found in both D-glucosamine hydrochloride ' and fructose, indicating that co-ordination engenders no significant additional strain.…”

Section: Resultsmentioning

confidence: 77%

Metal complexes of carbohydrates: isolation and characterisation of cobalt(III) complexes containing N-substituted glycosylamine ligands derived from ethane-1,2-diamine and glucosamine

Harrowfield¹,

Mocerino²,

Skelton³

et al. 1995

J. Chem. Soc., Dalton Trans.

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Reaction between cis-or trans- [Co(en),CI,] + (en = ethane-I ,2-diamine) and D-glucosamine (2-amino-2-deoxy-~-glucopyranose) in neutral aqueous solution results in a very complicated product mixture including as a major component several isomeric complex ions in which the co-ordination sphere is formally made up of two ethane-I ,2-diamine units and one sugar unit. Separation of these complexes by ion-exchange chromatography, and subsequent spectroscopic and structural studies have shown that they are diastereomeric forms in which the co-ordination sphere actually contains one bidentate ethane-1.2-diamine chelate and a multidentate ligand which is an N-(2'-aminoethyl)amino-substituted glycosylamine derived from glucosamine, fructosamine or mannosamine. The presence of the fructosamine moiety reveals that the complex formation reaction is accompanied by the Amadori rearrangement of glucosamine, while the presence of the mannosamine moiety indicates that this rearrangement may be reversible and possibly stereospecific in particular diastereoisomers. Crystal structure determinations have definitively characterised eight of the reaction products as: 1 a complex of the 1 -N-(2'-aminoethyl)amino-substituted glucosamine in which the sugar, although chelated to the metal as part of a tridentate ligand, is in its open-chain form and in which the four nitrogen atoms derived from the original two ethane-I ,2-diamine units are essentially coplanar; 2 a complex of tridentate 1 -N-(2'-aminoethyl)amino-substituted glucosamine in which the sugar has its pyranose form and the chelate edges spanned by the original ethane-I ,2-diamine units are in the A configuration; 3 a complex of 1 -N-(2'-aminoethyl)amino-substituted glucosamine in which the sugar is in its open-chain form and the ligand is bound in a quadridentate manner, with the chelate edges spanned by the original ethane-I ,2diamine units in the A configuration; 4 a complex of 1 -N-(2'-aminoethyl)amino-substituted mannosamine in which the sugar has a furanose form and is part of a quadridentate ligand, and the chelate edges spanned by the original ethane-1.2-diamine units are in the A configuration; 5 a complex of quadridentate 1 -(2'-aminoethylamino) -1 -deoxy-fructopyranosylamine in which the chelate edges spanned by the original ethane-1.2-diamine units are in the A configuration; 6 a complex of quadridentate 1 -(2'-aminoethylamino) -1 -deoxy-fructofuranosylamine in which the chelate edges spanned by the original ethane-l,2-diamine units are in the A configuration; 7 the same complex as 6 but in the form where its co-ordinated sugar hydroxyl group is deprotonated; and 8 a complex of 1 -(2'-aminoethylamino) -1 -deoxyfructopyranosylamine in which the chelate edges spanned by the original ethane-I ,2-diamine units are in the A configuration.

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“…The cationic complex, denoted [CoR] 3+ , of the title compound, (I), has been observed previously in three crystal structures: [CoR][C 8 H 4 O 12 Sb 2 ]ClÁ7H 2 O (Bernhardt et al, 2003), [CoR]Cl 3 Á2H 2 O (Clark et al, 1993) and [CoR][C 5 H 8 NS 2 ] 3 Á-5H 2 O (Achilleos et al, 1989). A similar N-deprotonated complex, [CoR]Cl 2 Á4H 2 O, has also been reported (Geue et al, 1984).…”

Section: Commentmentioning

confidence: 72%

“…By comparison, the chloride anions in the structure of [CoR]Cl 3 Á2H 2 O (Clark et al, 1993) occupy positions simlar to those occupied by bromide in [CoR]Br 3 . However, one chloride anion in [CoR]Cl 3 Á2H 2 O serves as a bridge between two NHÁ Á ÁNH edges in neighbouring complexes, thereby adopting essentially square-planar coordination.…”

Section: Commentmentioning

confidence: 99%

“…We are grateful to the Danish Natural Science Research Council (SNF) and Carlsbergfondet for provision of the X-ray equipment. Layers in the chloride salt [CoR]Cl 3 Á2H 2 O (Clark et al, 1993) lying parallel to the (110) planes. In this case, the C 4 axes of the central CoN 6 octahedra in each complex point approximately perpendicular to the layer plane, leaving gaps between the chloride anions that are occupied by water molecules.…”

Section: Figurementioning

confidence: 99%

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(1,8-Dinitro-3,6,10,13,16,19-hexaazabicyclo[6.6.6]icosane)cobalt(III) tribromide

2005

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Structural Characterization of Encapsulation Reactions Based on the Tris(ethane-1,2-diamine)cobalt(III) Ion

Cited by 25 publications

References 0 publications

A Functionalised Macrobicycle Complex Available for Surface Immobilisation and Protein Grafting

A Functionalised Macrobicycle Complex Available for Surface Immobilisation and Protein Grafting

Metal complexes of carbohydrates: isolation and characterisation of cobalt(III) complexes containing N-substituted glycosylamine ligands derived from ethane-1,2-diamine and glucosamine

(1,8-Dinitro-3,6,10,13,16,19-hexaazabicyclo[6.6.6]icosane)cobalt(III) tribromide

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