Favorable Protonation of the (μ-edt)[Fe 2 (PMe 3 ) 4 (CO) 2 (H-terminal)] + Hydrogenase Model Complex Over Its Bridging μ-H Counterpart: A Spectroscopic and DFT Study
dc.contributor.author | Galinato, Mary Grace I. | en_US |
dc.contributor.author | Whaley, C. Matthew | en_US |
dc.contributor.author | Roberts, Dean | en_US |
dc.contributor.author | Wang, Peng | en_US |
dc.contributor.author | Lehnert, Nicolai | en_US |
dc.date.accessioned | 2011-03-10T16:03:02Z | |
dc.date.accessioned | 2011-03-10T16:03:02Z | |
dc.date.available | 2012-04-30T18:27:22Z | en_US |
dc.date.issued | 2011-03 | en_US |
dc.identifier.citation | Galinato, Mary Grace I.; Whaley, C. Matthew; Roberts, Dean; Wang, Peng; Lehnert, Nicolai (2011). "Favorable Protonation of the (μ-edt)[Fe 2 (PMe 3 ) 4 (CO) 2 (H-terminal)] + Hydrogenase Model Complex Over Its Bridging μ-H Counterpart: A Spectroscopic and DFT Study." European Journal of Inorganic Chemistry 2011(7): 1147-1154. <http://hdl.handle.net/2027.42/83186> | en_US |
dc.identifier.issn | 1434-1948 | en_US |
dc.identifier.issn | 1099-0682 | en_US |
dc.identifier.uri | https://hdl.handle.net/2027.42/83186 | |
dc.description.abstract | The mechanism of hydrogen production in [FeFe] hydrogenase remains elusive. However, a species featuring a terminal hydride bound to the distal Fe is thought to be the key intermediate leading to hydrogen production. In this study, density functional theory (DFT) calculations on the terminal ( H -term) and bridging (μ-H) hydride isomers of (μ-edt)[Fe 2 (PMe 3 ) 4 (CO) 2 H] + are presented in order to understand the factors affecting their propensity for protonation. Relative to H -term, μ-H is 12.7 kcal/mol more stable, which contributes to its decreased reactivity towards an acid. Potential energy surface (PES) calculations for the reaction of the H -term isomer with 4-nitropyridinium, a proton source, further reveal a lower activation energy barrier (14.5 kcal/mol) for H -term than for μ-H (29 kcal/mol). Besides these energetic considerations, the H -term isomer displays a key molecular orbital (MO <139>) that has a relatively strong hydride (1s) contribution (23 %), which is not present in the μ-H isomer. This indicates a potential orbital control of the reaction of the hydride complexes with acid. The lower activation energy barrier and this key MO together control the overall catalytic activity of (μ-edt)[Fe 2 (PMe 3 ) 4 (CO) 2 (H-term)] + . Lastly, Raman and IR spectroscopy were performed in order to probe the ν (Fe-H) stretching mode of the two isomers and their deuterated counterparts. A ν (Fe-H) stretching mode was observed for the μ-H complex at 1220 cm –1 . However, the corresponding mode is not observed for the less stable H -term isomer. | en_US |
dc.publisher | WILEY-VCH Verlag | en_US |
dc.subject.other | Chemistry | en_US |
dc.subject.other | General Chemistry | en_US |
dc.title | Favorable Protonation of the (μ-edt)[Fe 2 (PMe 3 ) 4 (CO) 2 (H-terminal)] + Hydrogenase Model Complex Over Its Bridging μ-H Counterpart: A Spectroscopic and DFT Study | en_US |
dc.type | Article | en_US |
dc.rights.robots | IndexNoFollow | en_US |
dc.subject.hlbsecondlevel | Chemical Engineering | en_US |
dc.subject.hlbsecondlevel | Chemistry | en_US |
dc.subject.hlbsecondlevel | Materials Science and Engineering | en_US |
dc.subject.hlbtoplevel | Engineering | en_US |
dc.subject.hlbtoplevel | Science | en_US |
dc.description.peerreviewed | Peer Reviewed | en_US |
dc.contributor.affiliationum | Department of Chemistry, University of Michigan, Ann Arbor, MI 48109, USA, Fax: +1-734-615-3790 | en_US |
dc.contributor.affiliationum | Department of Chemistry, University of Michigan, Ann Arbor, MI 48109, USA, Fax: +1-734-615-3790 | en_US |
dc.contributor.affiliationother | Department of Chemistry, University of Illinois at Urbana-Champaign, Urbana, IL 61801, USA | en_US |
dc.contributor.affiliationother | Bruker Optics Inc. 19 Fortune Drive, Manning Park, Billerica, MA 01821, USA | en_US |
dc.contributor.affiliationother | Bruker Optics Inc. 19 Fortune Drive, Manning Park, Billerica, MA 01821, USA | en_US |
dc.identifier.pmid | 23162378 | en_US |
dc.description.bitstreamurl | http://deepblue.lib.umich.edu/bitstream/2027.42/83186/1/ejic_201001037_sm_miscellaneous_information.pdf | |
dc.description.bitstreamurl | http://deepblue.lib.umich.edu/bitstream/2027.42/83186/2/1147_ftp.pdf | |
dc.identifier.doi | 10.1002/ejic.201001037 | en_US |
dc.identifier.source | European Journal of Inorganic Chemistry | en_US |
dc.owningcollname | Interdisciplinary and Peer-Reviewed |
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