Conformational polymorphism and fluxional behaviour of M(PR3)2 units in closo-twelve-atom metallaheteroboranes with MX2B9(X = C or As) and MZB10 cages (Z = S, Se or Te)
Identifieur interne : 009633 ( Main/Merge ); précédent : 009632; suivant : 009634Conformational polymorphism and fluxional behaviour of M(PR3)2 units in closo-twelve-atom metallaheteroboranes with MX2B9(X = C or As) and MZB10 cages (Z = S, Se or Te)
Auteurs : Donnacha O'Connell ; Jennifer C. Patterson ; Trevor R. Spalding ; George Ferguson ; John F. Gallagher ; Yiwei Li ; John D. Kennedy ; Ram N Macías ; Mark Thornton-Pett ; Josef HolubSource :
- Journal of the Chemical Society, Dalton Transactions [ 0300-9246 ] ; 1996.
Abstract
The compounds [3,3-(PEt3)2-closo-3,1,2-PtAs2B9H9]1 and [2,2-(PMe2Ph)2-closo-2,1-PtSB10H10]2 were synthesised and characterised by NMR spectroscopy and X-ray crystallography. Crystals of 1 exhibit conformational polymorphism with five conformers of the Pt(PEt3)2 unit above the As2B3 face; those of 2 contain single conformers. The free energy of the barrier to rotation of the Pt(PMe2Ph)2 unit above the SB10 cage ligand in 2 has been determined in chloroform solution and is compared with data from other platinum and palladium metallaheteroboranes containing C2B9H11, As2B9H9, SeB10H10 and TeB10H10 ligands. A mechanism for the rotation of M(PR3)2 units above heteroborane ligand faces is suggested. It involves shifting the M(PR3)2 unit viaηn-bonded species (n < 5) with a concomitant twisting of the M(PR3)2 unit about an axis passing approximately through the metal atom and the antipodal B atom.
Url:
DOI: 10.1039/DT9960003323
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Spalding</name></author><author wicri:is="90%"><name sortKey="Ferguson, George" sort="Ferguson, George" uniqKey="Ferguson G" first="George" last="Ferguson">George Ferguson</name></author><author wicri:is="90%"><name sortKey="Gallagher, John F" sort="Gallagher, John F" uniqKey="Gallagher J" first="John F." last="Gallagher">John F. Gallagher</name></author><author wicri:is="90%"><name sortKey="Li, Yiwei" sort="Li, Yiwei" uniqKey="Li Y" first="Yiwei" last="Li">Yiwei Li</name></author><author wicri:is="90%"><name sortKey="Kennedy, John D" sort="Kennedy, John D" uniqKey="Kennedy J" first="John D." last="Kennedy">John D. Kennedy</name></author><author wicri:is="90%"><name sortKey="Macias, Ram N" sort="Macias, Ram N" uniqKey="Macias R" first="Ram N" last="Macías">Ram N Macías</name></author><author wicri:is="90%"><name sortKey="Thornton Pett, Mark" sort="Thornton Pett, Mark" uniqKey="Thornton Pett M" first="Mark" last="Thornton-Pett">Mark Thornton-Pett</name></author><author wicri:is="90%"><name sortKey="Holub, Josef" sort="Holub, Josef" uniqKey="Holub J" first="Josef" last="Holub">Josef Holub</name></author></titleStmt><publicationStmt><idno type="wicri:source">ISTEX</idno><idno type="RBID">ISTEX:28C2D372E9A4E2ED2C3AC703E2C02857B974A64B</idno><date when="1996" year="1996">1996</date><idno type="doi">10.1039/DT9960003323</idno><idno type="url">https://api.istex.fr/document/28C2D372E9A4E2ED2C3AC703E2C02857B974A64B/fulltext/pdf</idno><idno type="wicri:Area/Istex/Corpus">002730</idno><idno type="wicri:Area/Istex/Curation">002730</idno><idno type="wicri:Area/Istex/Checkpoint">003D69</idno><idno type="wicri:doubleKey">0300-9246:1996:O Connell D:conformational:polymorphism:and</idno><idno type="wicri:Area/Main/Merge">009633</idno></publicationStmt><sourceDesc><biblStruct><analytic><title level="a">Conformational polymorphism and fluxional behaviour of M(PR3)2 units in closo-twelve-atom metallaheteroboranes with MX2B9(X = C or As) and MZB10 cages (Z = S, Se or Te)</title><author wicri:is="90%"><name sortKey="O Connell, Donnacha" sort="O Connell, Donnacha" uniqKey="O Connell D" first="Donnacha" last="O'Connell">Donnacha O'Connell</name></author><author wicri:is="90%"><name sortKey="Patterson, Jennifer C" sort="Patterson, Jennifer C" uniqKey="Patterson J" first="Jennifer C." last="Patterson">Jennifer C. Patterson</name></author><author wicri:is="90%"><name sortKey="Spalding, Trevor R" sort="Spalding, Trevor R" uniqKey="Spalding T" first="Trevor R." last="Spalding">Trevor R. Spalding</name></author><author wicri:is="90%"><name sortKey="Ferguson, George" sort="Ferguson, George" uniqKey="Ferguson G" first="George" last="Ferguson">George Ferguson</name></author><author wicri:is="90%"><name sortKey="Gallagher, John F" sort="Gallagher, John F" uniqKey="Gallagher J" first="John F." last="Gallagher">John F. Gallagher</name></author><author wicri:is="90%"><name sortKey="Li, Yiwei" sort="Li, Yiwei" uniqKey="Li Y" first="Yiwei" last="Li">Yiwei Li</name></author><author wicri:is="90%"><name sortKey="Kennedy, John D" sort="Kennedy, John D" uniqKey="Kennedy J" first="John D." last="Kennedy">John D. Kennedy</name></author><author wicri:is="90%"><name sortKey="Macias, Ram N" sort="Macias, Ram N" uniqKey="Macias R" first="Ram N" last="Macías">Ram N Macías</name></author><author wicri:is="90%"><name sortKey="Thornton Pett, Mark" sort="Thornton Pett, Mark" uniqKey="Thornton Pett M" first="Mark" last="Thornton-Pett">Mark Thornton-Pett</name></author><author wicri:is="90%"><name sortKey="Holub, Josef" sort="Holub, Josef" uniqKey="Holub J" first="Josef" last="Holub">Josef Holub</name></author></analytic><monogr></monogr><series><title level="j">Journal of the Chemical Society, Dalton Transactions</title><title level="j" type="abbrev">J. Chem. Soc., Dalton Trans.</title><idno type="ISSN">0300-9246</idno><idno type="eISSN">1364-5447</idno><imprint><publisher>The Royal Society of Chemistry.</publisher><date type="published" when="1996">1996</date><biblScope unit="volume">0</biblScope><biblScope unit="issue">15</biblScope><biblScope unit="page" from="3323">3323</biblScope><biblScope unit="page" to="3333">3333</biblScope></imprint><idno type="ISSN">0300-9246</idno></series><idno type="istex">28C2D372E9A4E2ED2C3AC703E2C02857B974A64B</idno><idno type="DOI">10.1039/DT9960003323</idno><idno type="ms-id">DT9960003323</idno></biblStruct></sourceDesc><seriesStmt><idno type="ISSN">0300-9246</idno></seriesStmt></fileDesc><profileDesc><textClass></textClass><langUsage><language ident="en">en</language></langUsage></profileDesc></teiHeader><front><div type="abstract">The compounds [3,3-(PEt3)2-closo-3,1,2-PtAs2B9H9]1 and [2,2-(PMe2Ph)2-closo-2,1-PtSB10H10]2 were synthesised and characterised by NMR spectroscopy and X-ray crystallography. Crystals of 1 exhibit conformational polymorphism with five conformers of the Pt(PEt3)2 unit above the As2B3 face; those of 2 contain single conformers. The free energy of the barrier to rotation of the Pt(PMe2Ph)2 unit above the SB10 cage ligand in 2 has been determined in chloroform solution and is compared with data from other platinum and palladium metallaheteroboranes containing C2B9H11, As2B9H9, SeB10H10 and TeB10H10 ligands. A mechanism for the rotation of M(PR3)2 units above heteroborane ligand faces is suggested. It involves shifting the M(PR3)2 unit viaηn-bonded species (n < 5) with a concomitant twisting of the M(PR3)2 unit about an axis passing approximately through the metal atom and the antipodal B atom.</div></front></TEI></record>Pour manipuler ce document sous Unix (Dilib)
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