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Mechanistic studies on proton transfer in a [FeFe] hydrogenase mimic complex
KTH, School of Biotechnology (BIO), Theoretical Chemistry and Biology.
KTH, School of Biotechnology (BIO), Theoretical Chemistry and Biology.ORCID iD: 0000-0002-1553-4027
2013 (English)In: Dalton Transactions, ISSN 1477-9226, E-ISSN 1477-9234, Vol. 42, no 21, 7816-7822 p.Article in journal (Refereed) Published
Abstract [en]

Four different pathways for deprotonation of [(mu-pdt){Fe(CO)(3)}{Fe(CO)(kappa(2)-Me2PCH2N(Me)CH2PMe2)}] (pdt = propane-1,3-dithiolate) [1H(mu)](1+) were examined, including (1) the "Direct" deprotonation; (2) the "Indirect" deprotonation via the pendant amine N; (3) the "Indirect" deprotonation via the distal metal Fe; and (4) the "Indirect" deprotonation via the dithiolate S. Only deprotonation of the "Indirect" pathway via the pendant amine N is feasible at room temperature. The most favorable migration destination for the bridging hydride in [1H(mu)](1+) is the pendant amine N (activation energy barrier 16.1 kcal mol(-1)). Migrations to the other two possible sites including the distal metal Fe (34.6 kcal mol(-1)) and the S in the dithiolate group (41.5 kcal mol(-1)) were hindered by high proton shuttling barriers. Once the migration barriers of those three "Indirect" pathways are overcome, the following deprotonations from all three positions including the distal atom Fe, the dithiolate S and the pendant amine N, are all feasible. The results also demonstrate a large difference for deprotonation of the hydride from the terminal and bridging sites. The low energy of the virtual orbital associated with the antibonding M-H interaction of [1H(Fe)](1+) implies the high activity for the interaction with aniline.

Place, publisher, year, edition, pages
2013. Vol. 42, no 21, 7816-7822 p.
Keyword [en]
[FeFe]hydrogenases, Bridging hydride, Bridging sites, Mechanistic studies, Migration barriers, Pendant amines, Room temperature, Virtual orbitals
National Category
Chemical Sciences
Identifiers
URN: urn:nbn:se:kth:diva-123637DOI: 10.1039/c3dt33087gISI: 000318792400038Scopus ID: 2-s2.0-84877762775OAI: oai:DiVA.org:kth-123637DiVA: diva2:630247
Funder
Swedish Research Council
Note

QC 20130618

Available from: 2013-06-18 Created: 2013-06-13 Last updated: 2017-12-06Bibliographically approved
In thesis
1. Theoretical Studies on Water Splitting Using Transition Metal Complexes
Open this publication in new window or tab >>Theoretical Studies on Water Splitting Using Transition Metal Complexes
2014 (English)Doctoral thesis, comprehensive summary (Other academic)
Place, publisher, year, edition, pages
Stockholm: KTH Royal Institute of Technology, 2014. xii, 66 p.
Series
TRITA-BIO-Report, ISSN 1654-2312 ; 2014:6
National Category
Theoretical Chemistry
Identifiers
urn:nbn:se:kth:diva-145191 (URN)978-91-7595-069-3 (ISBN)
Public defence
2014-06-13, Albanova FB53, Roslagstullsbacken 21, Stockholm, 10:00 (English)
Opponent
Supervisors
Note

QC 20140526

Available from: 2014-05-26 Created: 2014-05-14 Last updated: 2014-05-26Bibliographically approved

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Ahlquist, Mårten S. G.

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