Source:http://linkedlifedata.com/resource/pubmed/id/15554651
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| Predicate | Object |
|---|---|
| rdf:type | |
| lifeskim:mentions | |
| pubmed:issue |
24
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| pubmed:dateCreated |
2004-11-23
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| pubmed:abstractText |
Phosphines are traditionally considered as Lewis bases or ligands in transition metal and main group complexes. Despite their electron-rich (lone pair-bearing) nature, an extensive coordination chemistry for Lewis acidic phosphorus centers is being developed; such chemistry provides a new synthetic approach for phosphorus-element bond formation, leading to new types of structures and modes of bonding. Complexes of Ph2P+ with a variety of donor elements (P, N, C) give experimentally short donor-acceptor bond lengths, when compared to other cationic phosphorus Lewis acid complexes. We have calculated that the energy of the lowest unoccupied molecular orbital (LUMO) in Ph2P+ is lower than that of (Me2N)2P+, which partially explains the greater exothermicity of reactions of donors with the diaryl acceptor. Furthermore, the energies required to distort the diphenylphosphenium cation from its ground-state geometry are significantly smaller than those of the diamido cations and, thus, enhance the exothermicity of donor coordination. These computational data, in conjunction with evidence from experimental solid-state structures, indicate that Ph2P+ is a significantly better Lewis acid relative to the more common diaminophosphenium analogues (R2N)2P+ and are used to elucidate the nature of the bonding in donor-phosphenium complexes.
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| pubmed:language |
eng
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| pubmed:journal | |
| pubmed:status |
PubMed-not-MEDLINE
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| pubmed:month |
Nov
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| pubmed:issn |
0020-1669
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| pubmed:author | |
| pubmed:issnType |
Print
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| pubmed:day |
29
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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 |
7857-67
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| pubmed:year |
2004
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| pubmed:articleTitle |
Computational insights into the acceptor chemistry of phosphenium cations.
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| pubmed:affiliation |
Department of Chemistry and Biochemistry, University of Windsor, Windsor, Ontario N9B 3P4, Canada.
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| pubmed:publicationType |
Journal Article
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