The free-energy barrier to hydride transfer across a dipalladium complex
We use density-functional theory molecular dynamics (DFT-MD) simulations to determine the hydride transfer coordinate between palladium centres of the crystallographically observed terminal hydride locations, Pd-Pd-H, originally postulated for the solution dynamics of the complex bis-NHC dipalladium...
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| Veröffentlicht in: | Faraday discussions 2015-01, Vol.177, p.99-19 |
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| creator | Vanston, C. R Kearley, G. J Edwards, A. J Darwish, T. A de Souza, N. R Ramirez-Cuesta, A. J Gardiner, M. G |
| description | We use density-functional theory molecular dynamics (DFT-MD) simulations to determine the hydride transfer coordinate between palladium centres of the crystallographically observed terminal hydride locations, Pd-Pd-H, originally postulated for the solution dynamics of the complex bis-NHC dipalladium hydride [{(MesIm)
2
CH
2
}
2
Pd
2
H][PF
6
], and then calculate the free-energy along this coordinate. We estimate the transfer barrier-height to be about 20 kcal mol
−1
with a hydride transfer rate in the order of seconds at room temperature. We validate our DFT-MD modelling using inelastic neutron scattering which reveals anharmonicity of the hydride environment that is so pronounced that there is complete failure of the harmonic model for the hydride ligand. The simulations are extended to high temperature to bring the H-transfer to a rate that is accessible to the simulation technique. |
| doi_str_mv | 10.1039/c4fd00182f |
| format | Article |
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2
CH
2
}
2
Pd
2
H][PF
6
], and then calculate the free-energy along this coordinate. We estimate the transfer barrier-height to be about 20 kcal mol
−1
with a hydride transfer rate in the order of seconds at room temperature. We validate our DFT-MD modelling using inelastic neutron scattering which reveals anharmonicity of the hydride environment that is so pronounced that there is complete failure of the harmonic model for the hydride ligand. The simulations are extended to high temperature to bring the H-transfer to a rate that is accessible to the simulation technique.</description><identifier>ISSN: 1359-6640</identifier><identifier>EISSN: 1364-5498</identifier><identifier>DOI: 10.1039/c4fd00182f</identifier><identifier>PMID: 25652724</identifier><language>eng</language><publisher>England: Royal Society of Chemistry</publisher><subject>Accessibility ; Anharmonicity ; Computer simulation ; Energy Transfer ; Failure ; Hydrides ; Hydrogen - chemistry ; INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY ; Kinetics ; Mathematical models ; Molecular dynamics ; Molecular Dynamics Simulation ; Palladium ; Palladium - chemistry ; Temperature ; Thermodynamics</subject><ispartof>Faraday discussions, 2015-01, Vol.177, p.99-19</ispartof><lds50>peer_reviewed</lds50><oa>free_for_read</oa><woscitedreferencessubscribed>false</woscitedreferencessubscribed><citedby>FETCH-LOGICAL-c468t-918c669d8a5c3038a00f5f9cabe97eb10aea990dec1e7d487ebb1b4855d862273</citedby><cites>FETCH-LOGICAL-c468t-918c669d8a5c3038a00f5f9cabe97eb10aea990dec1e7d487ebb1b4855d862273</cites></display><links><openurl>$$Topenurl_article</openurl><openurlfulltext>$$Topenurlfull_article</openurlfulltext><thumbnail>$$Tsyndetics_thumb_exl</thumbnail><link.rule.ids>230,315,782,786,887,27933,27934</link.rule.ids><backlink>$$Uhttps://www.ncbi.nlm.nih.gov/pubmed/25652724$$D View this record in MEDLINE/PubMed$$Hfree_for_read</backlink><backlink>$$Uhttps://www.osti.gov/servlets/purl/1336579$$D View this record in Osti.gov$$Hfree_for_read</backlink></links><search><creatorcontrib>Vanston, C. R</creatorcontrib><creatorcontrib>Kearley, G. J</creatorcontrib><creatorcontrib>Edwards, A. J</creatorcontrib><creatorcontrib>Darwish, T. A</creatorcontrib><creatorcontrib>de Souza, N. R</creatorcontrib><creatorcontrib>Ramirez-Cuesta, A. J</creatorcontrib><creatorcontrib>Gardiner, M. G</creatorcontrib><creatorcontrib>Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)</creatorcontrib><title>The free-energy barrier to hydride transfer across a dipalladium complex</title><title>Faraday discussions</title><addtitle>Faraday Discuss</addtitle><description>We use density-functional theory molecular dynamics (DFT-MD) simulations to determine the hydride transfer coordinate between palladium centres of the crystallographically observed terminal hydride locations, Pd-Pd-H, originally postulated for the solution dynamics of the complex bis-NHC dipalladium hydride [{(MesIm)
2
CH
2
}
2
Pd
2
H][PF
6
], and then calculate the free-energy along this coordinate. We estimate the transfer barrier-height to be about 20 kcal mol
−1
with a hydride transfer rate in the order of seconds at room temperature. We validate our DFT-MD modelling using inelastic neutron scattering which reveals anharmonicity of the hydride environment that is so pronounced that there is complete failure of the harmonic model for the hydride ligand. The simulations are extended to high temperature to bring the H-transfer to a rate that is accessible to the simulation technique.</description><subject>Accessibility</subject><subject>Anharmonicity</subject><subject>Computer simulation</subject><subject>Energy Transfer</subject><subject>Failure</subject><subject>Hydrides</subject><subject>Hydrogen - chemistry</subject><subject>INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY</subject><subject>Kinetics</subject><subject>Mathematical models</subject><subject>Molecular dynamics</subject><subject>Molecular Dynamics Simulation</subject><subject>Palladium</subject><subject>Palladium - chemistry</subject><subject>Temperature</subject><subject>Thermodynamics</subject><issn>1359-6640</issn><issn>1364-5498</issn><fulltext>true</fulltext><rsrctype>article</rsrctype><creationdate>2015</creationdate><recordtype>article</recordtype><sourceid>EIF</sourceid><recordid>eNqF0UtLAzEQB_AgitbHxbuyehJhNdk8NjlKtVYQvOg5ZJOJXek-TLZgv72xrXrTU4aZH0OYP0LHBF8RTNW1Zd5hTGTht9CIUMFyzpTc_qq5yoVgeA_tx_iGMRZpuov2Ci54URZshKbPM8h8AMihhfC6zCoTQg0hG7pstnShdpANwbTRp56xoYsxM5mrezOfG1cvmsx2TT-Hj0O04808wtHmPUAvk7vn8TR_fLp_GN885pYJOeSKSCuEctJwSzGVBmPPvbKmAlVCRbABoxR2YAmUjsnUq0jFJOdOiqIo6QE6X-_t4lDraOsB7Mx2bQt20IRSwUuV0MUa9aF7X0AcdFNHC-nLLXSLqInEmNGCUPY_FSWlJUtHTPRyTVdnCOB1H-rGhKUmWH8locdscrtKYpLw6WbvomrA_dDv0ydwtgYh2p_pb5S6dz6Zk78M_QQfSJd-</recordid><startdate>20150101</startdate><enddate>20150101</enddate><creator>Vanston, C. R</creator><creator>Kearley, G. J</creator><creator>Edwards, A. J</creator><creator>Darwish, T. A</creator><creator>de Souza, N. R</creator><creator>Ramirez-Cuesta, A. J</creator><creator>Gardiner, M. G</creator><general>Royal Society of Chemistry</general><scope>CGR</scope><scope>CUY</scope><scope>CVF</scope><scope>ECM</scope><scope>EIF</scope><scope>NPM</scope><scope>AAYXX</scope><scope>CITATION</scope><scope>7X8</scope><scope>7SR</scope><scope>8BQ</scope><scope>8FD</scope><scope>JG9</scope><scope>OIOZB</scope><scope>OTOTI</scope></search><sort><creationdate>20150101</creationdate><title>The free-energy barrier to hydride transfer across a dipalladium complex</title><author>Vanston, C. R ; Kearley, G. J ; Edwards, A. J ; Darwish, T. A ; de Souza, N. R ; Ramirez-Cuesta, A. J ; Gardiner, M. G</author></sort><facets><frbrtype>5</frbrtype><frbrgroupid>cdi_FETCH-LOGICAL-c468t-918c669d8a5c3038a00f5f9cabe97eb10aea990dec1e7d487ebb1b4855d862273</frbrgroupid><rsrctype>articles</rsrctype><prefilter>articles</prefilter><language>eng</language><creationdate>2015</creationdate><topic>Accessibility</topic><topic>Anharmonicity</topic><topic>Computer simulation</topic><topic>Energy Transfer</topic><topic>Failure</topic><topic>Hydrides</topic><topic>Hydrogen - chemistry</topic><topic>INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY</topic><topic>Kinetics</topic><topic>Mathematical models</topic><topic>Molecular dynamics</topic><topic>Molecular Dynamics Simulation</topic><topic>Palladium</topic><topic>Palladium - chemistry</topic><topic>Temperature</topic><topic>Thermodynamics</topic><toplevel>peer_reviewed</toplevel><toplevel>online_resources</toplevel><creatorcontrib>Vanston, C. R</creatorcontrib><creatorcontrib>Kearley, G. J</creatorcontrib><creatorcontrib>Edwards, A. J</creatorcontrib><creatorcontrib>Darwish, T. A</creatorcontrib><creatorcontrib>de Souza, N. R</creatorcontrib><creatorcontrib>Ramirez-Cuesta, A. J</creatorcontrib><creatorcontrib>Gardiner, M. G</creatorcontrib><creatorcontrib>Oak Ridge National Lab. 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(ORNL), Oak Ridge, TN (United States)</aucorp><format>journal</format><genre>article</genre><ristype>JOUR</ristype><atitle>The free-energy barrier to hydride transfer across a dipalladium complex</atitle><jtitle>Faraday discussions</jtitle><addtitle>Faraday Discuss</addtitle><date>2015-01-01</date><risdate>2015</risdate><volume>177</volume><spage>99</spage><epage>19</epage><pages>99-19</pages><issn>1359-6640</issn><eissn>1364-5498</eissn><abstract>We use density-functional theory molecular dynamics (DFT-MD) simulations to determine the hydride transfer coordinate between palladium centres of the crystallographically observed terminal hydride locations, Pd-Pd-H, originally postulated for the solution dynamics of the complex bis-NHC dipalladium hydride [{(MesIm)
2
CH
2
}
2
Pd
2
H][PF
6
], and then calculate the free-energy along this coordinate. We estimate the transfer barrier-height to be about 20 kcal mol
−1
with a hydride transfer rate in the order of seconds at room temperature. We validate our DFT-MD modelling using inelastic neutron scattering which reveals anharmonicity of the hydride environment that is so pronounced that there is complete failure of the harmonic model for the hydride ligand. The simulations are extended to high temperature to bring the H-transfer to a rate that is accessible to the simulation technique.</abstract><cop>England</cop><pub>Royal Society of Chemistry</pub><pmid>25652724</pmid><doi>10.1039/c4fd00182f</doi><tpages>11</tpages><oa>free_for_read</oa></addata></record> |
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| ispartof | Faraday discussions, 2015-01, Vol.177, p.99-19 |
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| language | eng |
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| source | MEDLINE; Royal Society Of Chemistry Journals; Alma/SFX Local Collection |
| subjects | Accessibility Anharmonicity Computer simulation Energy Transfer Failure Hydrides Hydrogen - chemistry INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY Kinetics Mathematical models Molecular dynamics Molecular Dynamics Simulation Palladium Palladium - chemistry Temperature Thermodynamics |
| title | The free-energy barrier to hydride transfer across a dipalladium complex |
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