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Formation of metallacarboxylic acids through Hieber base reaction. A density functional theory study
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dc.contributor.author | Ahmad, Shahbaz | |
dc.contributor.author | Berry, Elizabeth | |
dc.contributor.author | Boyle, Conor | |
dc.contributor.author | Hudson, Christopher | |
dc.contributor.author | Ireland, Oliver W. | |
dc.contributor.author | Thompson, Emily A. | |
dc.contributor.author | Buehl, Michael | |
dc.date.accessioned | 2019-01-28T11:30:08Z | |
dc.date.available | 2019-01-28T11:30:08Z | |
dc.date.issued | 2019-02 | |
dc.identifier | 256992172 | |
dc.identifier | 375c7a5a-0def-46c3-b161-9e8a959c00ca | |
dc.identifier | 85060544253 | |
dc.identifier | 000456664900002 | |
dc.identifier.citation | Ahmad , S , Berry , E , Boyle , C , Hudson , C , Ireland , O W , Thompson , E A & Buehl , M 2019 , ' Formation of metallacarboxylic acids through Hieber base reaction. A density functional theory study ' , Journal of Molecular Modeling , vol. 25 , 45 . https://doi.org/10.1007/s00894-018-3915-1 | en |
dc.identifier.issn | 1610-2940 | |
dc.identifier.other | ORCID: /0000-0002-1095-7143/work/53548918 | |
dc.identifier.uri | https://hdl.handle.net/10023/16940 | |
dc.description | We thank EaStCHEM and the School of Chemistry for support. | en |
dc.description.abstract | Using density functional theory (B97-D/ECP2/PCM//RI-BP86/ECP1 level), we have studied the effects of ligand variation on OH− uptake by transition-metal carbonyls (Hieber base reaction), i.e., LnM(CO) + OH− → [LnM(CO2H)]−, M = Fe, Ru, Os, L = CO, PMe3, PF3, py, bipy, Cl, H. The viability of this step depends notably on the nature of the co-ligands, and a large span of driving forces is predicted, ranging from ΔG = −144 kJ/mol to +122 kJ/mol. Based on evaluation of atomic charges from natural population analysis, it is the ability of the co-ligands to delocalize the additional negative charge (through their π-acidity) that is the key factor affecting the driving force for OH− uptake. Implications for the design of new catalysts for water gas shift reaction are discussed. | |
dc.format.extent | 8 | |
dc.format.extent | 1509504 | |
dc.language.iso | eng | |
dc.relation.ispartof | Journal of Molecular Modeling | en |
dc.subject | Homogeneous catalysis | en |
dc.subject | Water gas shift reaction | en |
dc.subject | Hieber base reaction | en |
dc.subject | Density functional theory | en |
dc.subject | QD Chemistry | en |
dc.subject | NDAS | en |
dc.subject.lcc | QD | en |
dc.title | Formation of metallacarboxylic acids through Hieber base reaction. A density functional theory study | en |
dc.type | Journal article | en |
dc.contributor.institution | University of St Andrews. School of Chemistry | en |
dc.contributor.institution | University of St Andrews. EaSTCHEM | en |
dc.identifier.doi | 10.1007/s00894-018-3915-1 | |
dc.description.status | Peer reviewed | en |
dc.date.embargoedUntil | 2019-01-25 |
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