Reversible Photoinduced Reductive Elimination of H2 from the Nitrogenase Dihydride State, the E(4)(4H) Janus Intermediate

Journal of the American Chemical Society
Dmitriy LukoyanovBrian M Hoffman

Abstract

We recently demonstrated that N2 reduction by nitrogenase involves the obligatory release of one H2 per N2 reduced. These studies focus on the E4(4H) "Janus intermediate", which has accumulated four reducing equivalents as two [Fe-H-Fe] bridging hydrides. E4(4H) is poised to bind and reduce N2 through reductive elimination (re) of the two hydrides as H2, coupled to the binding/reduction of N2. To obtain atomic-level details of the re activation process, we carried out in situ 450 nm photolysis of E4(4H) in an EPR cavity at temperatures below 20 K. ENDOR and EPR measurements show that photolysis generates a new FeMo-co state, denoted E4(2H)*, through the photoinduced re of the two bridging hydrides of E4(4H) as H2. During cryoannealing at temperatures above 175 K, E4(2H)* reverts to E4(4H) through the oxidative addition (oa) of the H2. The photolysis quantum yield is temperature invariant at liquid helium temperatures and shows a rather large kinetic isotope effect, KIE = 10. These observations imply that photoinduced release of H2 involves a barrier to the combination of the two nascent H atoms, in contrast to a barrierless process for monometallic inorganic complexes, and further suggest that H2 formation involves nuclear tunn...Continue Reading

References

Nov 7, 1996·Chemical Reviews·Barbara K. Burgess, David J. Lowe
Apr 28, 2005·Journal of the American Chemical Society·Robert Y IgarashiBrian M Hoffman
Jan 19, 2006·Journal of the American Chemical Society·Jeremy M SmithPatrick L Holland
Jul 18, 2006·Inorganic Chemistry·Ying YuPatrick L Holland
Jan 26, 2007·Proceedings of the National Academy of Sciences of the United States of America·Dmitriy LukoyanovBrian M Hoffman
May 1, 2008·Journal of the American Chemical Society·Ying YuPatrick L Holland
Jun 6, 2009·Annual Review of Biochemistry·Lance C SeefeldtDennis R Dean
Feb 4, 2010·Journal of the American Chemical Society·Dmitriy LukoyanovBrian M Hoffman
Feb 4, 2010·Chemical Communications : Chem Comm·Joachim BallmannMichael D Fryzuk
Feb 18, 2010·Journal of Organometallic Chemistry·Thomas R Dugan, Patrick L Holland
Oct 1, 2011·Journal of the American Chemical Society·Yunho LeeJonas C Peters
Nov 15, 2012·Proceedings of the National Academy of Sciences of the United States of America·Zhi-Yong YangLance C Seefeldt
Jan 8, 2013·Accounts of Chemical Research·Brian M HoffmanLance C Seefeldt
Apr 20, 2013·Biochimica Et Biophysica Acta·Lance C SeefeldtDennis R Dean
Sep 26, 2013·Proceedings of the National Academy of Sciences of the United States of America·Zhi-Yong YangLance C Seefeldt
Sep 26, 2013·Proceedings of the National Academy of Sciences of the United States of America·Simon DuvalLance C Seefeldt
Jan 29, 2014·Chemical Reviews·Brian M HoffmanLance C Seefeldt
Mar 25, 2014·Chemical Reviews·Wolfgang LubitzEdward Reijerse
Sep 23, 2014·Journal of the American Chemical Society·William A GundersonBrian M Hoffman

❮ Previous
Next ❯

Citations

May 14, 2016·Journal of the American Chemical Society·Ilija Čorić, Patrick L Holland
Jul 7, 2016·Chemical Reviews·Robin N Perutz, Barbara Procacci
May 11, 2017·Angewandte Chemie·Trixia M BuscaganJonas C Peters
Jul 21, 2017·Inorganic Chemistry·Nicholas A ArnetPatrick L Holland
Aug 24, 2017·Chemphyschem : a European Journal of Chemical Physics and Physical Chemistry·Yoann RouxMarcello Gennari
Jul 22, 2016·Dalton Transactions : an International Journal of Inorganic Chemistry·David M Ermert, Leslie J Murray
Nov 1, 2017·Proceedings of the National Academy of Sciences of the United States of America·Shengda DingMichael B Hall
Dec 6, 2019·Chembiochem : a European Journal of Chemical Biology·Ian Dance
Mar 18, 2020·Chemistry : a European Journal·Kodai IshiharaYasuhiro Ohki
Dec 4, 2019·European Journal of Inorganic Chemistry·Dae Ho Hong, Leslie J Murray
Mar 31, 2018·Science·Daniel SippelOliver Einsle
Jul 22, 2020·Chemical Communications : Chem Comm·Yasuhiro OhkiRoger E Cramer
Aug 21, 2018·Chemical Science·Meaghan M Deegan, Jonas C Peters
Jan 31, 2020·Chemical Reviews·Hannah L Rutledge, F Akif Tezcan
Mar 17, 2020·Chemical Reviews·Lance C SeefeldtBrian M Hoffman
Apr 3, 2020·Chemical Reviews·Casey Van StappenSerena DeBeer
Oct 18, 2020·Journal of Inorganic Biochemistry·Derek F HarrisLance C Seefeldt
Sep 12, 2018·Current Opinion in Chemical Biology·Lance C SeefeldtBrian M Hoffman
Dec 11, 2017·Bioelectrochemistry·Bo HuLance C Seefeldt
Jun 17, 2020·Chemical Reviews·Oliver Einsle, Douglas C Rees
Sep 12, 2019·Journal of the American Chemical Society·Hao YangBrian M Hoffman
Apr 15, 2020·Journal of the American Chemical Society·Charles H Arnett, Theodor Agapie
Sep 25, 2019·The Journal of Physical Chemistry. B·Dmitriy A LukoyanovBrian M Hoffman
Aug 31, 2017·Journal of the American Chemical Society·Nimesh KhadkaLance C Seefeldt
Dec 24, 2018·ACS Catalysis·Ricardo B FerreiraLeslie J Murray
Jul 3, 2018·Biochemistry·Michael RohdeOliver Einsle
Oct 14, 2021·Chembiochem : a European Journal of Chemical Biology·Niels N Oehlmann, Johannes G Rebelein
Dec 4, 2021·Dalton Transactions : an International Journal of Inorganic Chemistry·Ian Dance

❮ Previous
Next ❯

Related Concepts

Trending Feeds

COVID-19

Coronaviruses encompass a large family of viruses that cause the common cold as well as more serious diseases, such as the ongoing outbreak of coronavirus disease 2019 (COVID-19; formally known as 2019-nCoV). Coronaviruses can spread from animals to humans; symptoms include fever, cough, shortness of breath, and breathing difficulties; in more severe cases, infection can lead to death. This feed covers recent research on COVID-19.

Blastomycosis

Blastomycosis fungal infections spread through inhaling Blastomyces dermatitidis spores. Discover the latest research on blastomycosis fungal infections here.

Nuclear Pore Complex in ALS/FTD

Alterations in nucleocytoplasmic transport, controlled by the nuclear pore complex, may be involved in the pathomechanism underlying multiple neurodegenerative diseases including Amyotrophic Lateral Sclerosis and Frontotemporal Dementia. Here is the latest research on the nuclear pore complex in ALS and FTD.

Applications of Molecular Barcoding

The concept of molecular barcoding is that each original DNA or RNA molecule is attached to a unique sequence barcode. Sequence reads having different barcodes represent different original molecules, while sequence reads having the same barcode are results of PCR duplication from one original molecule. Discover the latest research on molecular barcoding here.

Chronic Fatigue Syndrome

Chronic fatigue syndrome is a disease characterized by unexplained disabling fatigue; the pathology of which is incompletely understood. Discover the latest research on chronic fatigue syndrome here.

Evolution of Pluripotency

Pluripotency refers to the ability of a cell to develop into three primary germ cell layers of the embryo. This feed focuses on the mechanisms that underlie the evolution of pluripotency. Here is the latest research.

Position Effect Variegation

Position Effect Variagation occurs when a gene is inactivated due to its positioning near heterochromatic regions within a chromosome. Discover the latest research on Position Effect Variagation here.

STING Receptor Agonists

Stimulator of IFN genes (STING) are a group of transmembrane proteins that are involved in the induction of type I interferon that is important in the innate immune response. The stimulation of STING has been an active area of research in the treatment of cancer and infectious diseases. Here is the latest research on STING receptor agonists.

Microbicide

Microbicides are products that can be applied to vaginal or rectal mucosal surfaces with the goal of preventing, or at least significantly reducing, the transmission of sexually transmitted infections. Here is the latest research on microbicides.

Related Papers

Accounts of Chemical Research
Brian M HoffmanLance C Seefeldt
Proceedings of the National Academy of Sciences of the United States of America
Zhi-Yong YangLance C Seefeldt
Proceedings of the National Academy of Sciences of the United States of America
Dmitriy LukoyanovBrian M Hoffman
© 2022 Meta ULC. All rights reserved