Source:http://linkedlifedata.com/resource/pubmed/id/19130436
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| Predicate | Object |
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| rdf:type | |
| lifeskim:mentions | |
| pubmed:issue |
3
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| pubmed:dateCreated |
2009-3-2
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| pubmed:abstractText |
A combined experimental/theoretical study provides insight into the bridging coordination of M-Cl bonds with the ambiphilic phosphine-borane ligands iPr(2)P-o(C(6)H(4))-BR(2) (PBCy(2): R = Cy; PBMes(2): R = Mes). Reaction of [PdCl(allyl)(PBCy(2))] (3) with HCl affords the related dinuclear complex [PdCl(mu-Cl)(PBCy(2))](2) (5). Subsequent cleavage of the chloride bridge by PPh(3) leads to the heteroleptic mononuclear complex trans-[PdCl(2)(PPh(3))(PBCy(2))] (6). The solid-state structures of complexes 5 and 6 substantiate the propensity of the PBCy(2) ligand to bridge Pd-Cl bonds via P-->Pd--Cl-->B interactions. DFT calculations carried out on both the model mononuclear complexes 3* and 6* reveal that in each system the energy of the linkage isomer with a Cl-->B interaction is very similar to that without. A comparison of the solution and solid-state (11)B NMR spectroscopic data for complexes 3 and 6 suggests the possible interconversion of the bridging and B-pendant forms in solution. Bridging coordination of the PBCy(2) ligand across a Rh-Cl bond is observed in the solid-state structure of the related complex [RhCl(nbd)(PBCy(2))] (7). Replacement of the Cy groups at boron by Mes substituents illustrates the role of steric factors on the participation of the Lewis acid upon coordination, no Cl-->B interaction being observed in the complex [PdCl(allyl)(PBMes(2))] (8).
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| pubmed:language |
eng
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| pubmed:journal | |
| pubmed:status |
PubMed-not-MEDLINE
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| pubmed:month |
Mar
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| pubmed:issn |
1861-471X
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| pubmed:author | |
| pubmed:issnType |
Electronic
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| pubmed:day |
2
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| pubmed:volume |
4
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| pubmed:owner |
NLM
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| pubmed:authorsComplete |
Y
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| pubmed:pagination |
428-35
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| pubmed:year |
2009
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| pubmed:articleTitle |
Bridging M-Cl bonds with ambiphilic phosphine-borane ligands.
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| pubmed:affiliation |
Laboratoire Hétérochimie Fondamentale et Appliquée du CNRS (UMR 5069), Equipe Ligands Bifonctionnels et Polymères Biodégradables, Université Paul Sabatier, 118 route de Narbonne, 31062 Toulouse Cedex 09, France.
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| pubmed:publicationType |
Journal Article
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