Source:http://linkedlifedata.com/resource/pubmed/id/14753814
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| Predicate | Object |
|---|---|
| rdf:type | |
| lifeskim:mentions | |
| pubmed:issue |
3
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| pubmed:dateCreated |
2004-2-2
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| pubmed:abstractText |
The reaction of di-tert-butyl phosphate (((t)BuO)(2)P(O)(OH), dtbp-H) with copper acetate in the presence of pyridine (py) and 2,4,6-trimethylpyridine (collidine) has been investigated. Copper acetate reacts with dtbp-H in a reaction medium containing pyridine, DMSO, THF, and CH(3)OH to yield a one-dimensional polymeric complex [Cu(dtbp)(2)(py)(2)(mu-OH(2))](n) (1) as blue hollow crystalline tubes. The copper atoms in 1 are octahedral and are surrounded by two terminal phosphate ligands, two pyridine molecules, and two bridging water molecules. The mu-OH(2) ligands that are present along the elongated Jahn-Teller axis are responsible for the formation of the one-dimensional polymeric structure. Recrystallization of 1 in a DMSO/THF/CH(3)OH mixture results in the reorganization of the polymer and its conversion to a more stable tetranuclear copper cluster [Cu(4)(mu(3)-OH)(2)(dtbp)(6)(py)(2)] (2) in about 60% yield. The molecular structure of 2 is made up of a tetranuclear core [Cu(4)(mu(3)-OH)(2)] which is surrounded by six bidentate bridging dtbp ligands. While two of the copper atoms are pentacoordinate with a tbp geometry, the other two copper atoms exhibit a pseudooctahedral geometry with five normal Cu-O bonds and an elongated Cu-O linkage. The pentacoordinate copper centers bear an axial pyridine ligand. The short Cu.Cu nonbonded distances in the tetranuclear core of 2 lead to magnetic ordering at low temperature with an antiferromagnetic coupling at approximately 20 K (J(P) = -44 cm(-1), J(c) = -66 cm(-1), g = 2.25, and rho = 0.8%). When the reaction between di-tert-butyl phosphate (dtbp-H) and copper acetate was carried out in the presence of collidine, large dark-blue crystals of monomeric copper complex [Cu(dtbp)(2)(collidine)(2)] (3) formed as the only product. A single-crystal X-ray diffraction study of 3 reveals a slightly distorted square-planar geometry around the copper atom. Thermogravimetric analysis of 1-3 revealed a facile decomposition of the coordinated ligands and dtbp to produce a copper phosphate material around 500 degrees C. An independent solid-state thermolysis of all the three complexes in bulk at 500-510 degrees C for 2 days produced copper pyrophosphate Cu(2)P(2)O(7) along with small quantities of Cu(PO(3))(2) as revealed by DR-UV spectroscopic and PXRD studies.
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| pubmed:language |
eng
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| pubmed:journal | |
| pubmed:status |
PubMed-not-MEDLINE
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| pubmed:month |
Feb
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| pubmed:issn |
0020-1669
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| pubmed:author | |
| pubmed:issnType |
Print
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| pubmed:day |
9
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| pubmed:volume |
43
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| pubmed:owner |
NLM
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| pubmed:authorsComplete |
Y
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| pubmed:pagination |
945-53
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| pubmed:year |
2004
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| pubmed:articleTitle |
Monomeric, tetrameric, and polymeric copper di-tert-butyl phosphate complexes containing pyridine ancillary ligands.
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| pubmed:affiliation |
Department of Chemistry, Indian Institute of Technology-Bombay, Powai, Mumbai-400 076, India. rmv@iitb.ac.in
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| pubmed:publicationType |
Journal Article
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