Source:http://linkedlifedata.com/resource/pubmed/id/18802610
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rdf:type | |
lifeskim:mentions | |
pubmed:issue |
37
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pubmed:dateCreated |
2008-9-19
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pubmed:abstractText |
The syntheses and X-ray structures of [Co(Me-tpa)O2COZnCl3], [Co(pmea)O2COZnCl3].H2O [Co(trpyn)O2COZn(OH2)4OCO2Co(trpyn)](ZnCl4)2.H2O, [Co(trpyn)(O2COH)]ZnCl(4).3H2O and [Co(trpyn)(O2CO)]ClO4 are reported (Me-tpa=[(6-methyl-2-pyridyl)methyl]bis(2-pyridylmethyl)amine, pmea=bis(2-pyridylmethyl)-2-(2-pyridylethyl)amine, trpyn=tris(2-(1-pyrazolyl)ethyl)amine). The chelated bicarbonate complex [Co(trpyn)(O2COH)]ZnCl(4).3H2O is isolated as a crystalline solid from an acidic solution of the parent carbonate [Co(trpyn)(O2CO)]ClO4, and X-ray structural analysis shows that lengthening of the C=Oexo bond and shortening of the C-Oendo bond accompanies protonation. The bimetallic complex [Co(Me-tpa)O2COZnCl3] results from the unexpected coordination of ZnCl3- to the exo O atom of a chelated carbonate ligand. This complex is obtained from both acidic and neutral solutions in which [Zn2+]=1.0 M, while the structurally similar complex [Co(pmea)O2COZnCl3].H2O is isolated from an analogous neutral solution. The trimetallic complex [Co(trpyn)O2COZn(OH2)4OCO2Co(trpyn)](ZnCl4)2.H2O crystallises on prolonged standing of [Co(trpyn)(O2CO)]ClO4 in a neutral solution having [Zn2+]=1.0 M. The Zn-O bond lengths in all three complexes are indicative of bonds of significant strength. DFT calculations show that the nature of the bonding interaction between the Co(III) ion and the endo O atoms of the carbonate ligand remain essentially unaffected by coordination of Zn2+ to the exo O atom. They also show that such coordination of Zn2+ decreases the C-Oexo bond order.
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pubmed:language |
eng
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pubmed:journal | |
pubmed:citationSubset |
IM
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pubmed:chemical |
http://linkedlifedata.com/resource/pubmed/chemical/Carbonates,
http://linkedlifedata.com/resource/pubmed/chemical/Chelating Agents,
http://linkedlifedata.com/resource/pubmed/chemical/Cobalt,
http://linkedlifedata.com/resource/pubmed/chemical/Ligands,
http://linkedlifedata.com/resource/pubmed/chemical/Organometallic Compounds,
http://linkedlifedata.com/resource/pubmed/chemical/Protons,
http://linkedlifedata.com/resource/pubmed/chemical/Solutions,
http://linkedlifedata.com/resource/pubmed/chemical/Water
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pubmed:status |
MEDLINE
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pubmed:month |
Oct
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pubmed:issn |
1477-9226
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pubmed:author | |
pubmed:issnType |
Print
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pubmed:day |
7
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pubmed:owner |
NLM
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pubmed:authorsComplete |
Y
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pubmed:pagination |
4984-92
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pubmed:meshHeading |
pubmed-meshheading:18802610-Carbonates,
pubmed-meshheading:18802610-Chelating Agents,
pubmed-meshheading:18802610-Cobalt,
pubmed-meshheading:18802610-Crystallography, X-Ray,
pubmed-meshheading:18802610-Ligands,
pubmed-meshheading:18802610-Models, Chemical,
pubmed-meshheading:18802610-Models, Molecular,
pubmed-meshheading:18802610-Molecular Structure,
pubmed-meshheading:18802610-Organometallic Compounds,
pubmed-meshheading:18802610-Protons,
pubmed-meshheading:18802610-Solutions,
pubmed-meshheading:18802610-Stereoisomerism,
pubmed-meshheading:18802610-Water
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pubmed:year |
2008
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pubmed:articleTitle |
The donor ability of the chelated carbonate ligand: protonation and metallation of [(L)Co(O2CO)]+ complexes in aqueous solution.
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pubmed:affiliation |
Department of Chemistry, University of Otago, P.O. Box 56, Dunedin, New Zealand.
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pubmed:publicationType |
Journal Article,
Research Support, Non-U.S. Gov't
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