Photocatalytic hydrogen evolution using a Ru(II)-bound heteroaromatic ligand as a reactive site

Dalton Transactions : an International Journal of Inorganic Chemistry
Takuya SawakiTakahiko Kojima

Abstract

A RuII complex, [RuII(tpphz)(bpy)2]2+ (1) (tpphz = tetrapyridophenazine, bpy = 2,2'-bipyridine), whose tpphz ligand has a pyrazine moiety, is converted efficiently to [RuII(tpphz-HH)(bpy)2]2+ (2) having a dihydropyrazine moiety upon photoirradiation of a water-methanol mixed solvent solution of 1 in the presence of an electron donor. In this reaction, the triplet metal-to-ligand charge-transfer excited state (3MLCT*) of 1 is firstly formed upon photoirradiation and the 3MLCT* state is reductively quenched with an electron donor to afford [RuII(tpphz˙-)(bpy)2]+, which is converted to 2 without the observation of detectable reduced intermediates by nano-second laser flash photolysis. The inverse kinetic isotope effect (KIE) was observed to be 0.63 in the N-H bond formation of 2 at the dihydropyrazine moiety. White-light (380-670 nm) irradiation of a solution of 1 in a protic solvent, in the presence of an electron donor under an inert atmosphere, led to photocatalytic H2 evolution and the hydrogenation of organic substrates. In the reactions, complex 2 is required to be excited to form its 3MLCT* state to react with a proton and aldehydes. In photocatalytic H2 evolution, the H-H bond formation between photoexcited 2 and a proton ...Continue Reading

References

Oct 1, 1994·Free Radical Biology & Medicine·B S WinklerT S Rex
Jan 3, 1997·Science·N H DamrauerJ K McCusker
Sep 15, 1988·Physical Review A: General Physics·A D Becke
Nov 20, 2001·Chemical Reviews·M Yagi, M Kaneko
May 19, 2005·Journal of the American Chemical Society·Jonas I GoldsmithStefan Bernhard
Aug 4, 2005·Journal of the American Chemical Society·Yao LiuClaudia Turro
Aug 12, 2005·Chemical Reviews·Jacopo TomasiRoberto Cammi
May 15, 2007·Journal of the American Chemical Society·Javier J ConcepcionThomas J Meyer
May 29, 2007·Inorganic Chemistry·Olivier HamelinMarc Fontecave
Sep 13, 2007·Journal of Computational Chemistry·Noel M O'BoyleKarol M Langner
Oct 12, 2007·Chemical Reviews·Arthur J Esswein, Daniel G Nocera
Nov 15, 2007·Chemical Reviews·My Hang V Huynh, Thomas J Meyer
Jun 25, 2008·Inorganic Chemistry·Yujie SunClaudia Turro
Jul 9, 2008·ChemSusChem·Vincenzo BalzaniMargherita Venturi
Nov 11, 2008·Nature Materials·Xinchen WangMarkus Antonietti
Jun 25, 2009·Chemical Society Reviews·Davide RavelliAngelo Albini
Jul 2, 2009·Journal of the American Chemical Society·Theodore LazaridesRichard Eisenberg
Oct 8, 2009·Accounts of Chemical Research·Sharon Hammes-Schiffer
Nov 26, 2009·Inorganic Chemistry·Takashi FukushimaKoji Tanaka
Dec 1, 2009·Angewandte Chemie·Kirsten Zeitler
Sep 11, 2010·Dalton Transactions : an International Journal of Inorganic Chemistry·Takashi FukushimaKoji Tanaka
Oct 12, 2010·Chemical Reviews·Jeffrey J WarrenJames M Mayer
Oct 28, 2010·Accounts of Chemical Research·James M Mayer
Feb 1, 2008·Coordination Chemistry Reviews·Sharon Hammes-SchifferAlexander V Soudackov
Nov 19, 2010·Chemical Reviews·Jillian L DempseyHarry B Gray
Dec 17, 2010·Nature Chemistry·Shunichi FukuzumiWonwoo Nam
Feb 19, 2011·Journal of the American Chemical Society·Hiroaki KotaniShunichi Fukuzumi
May 10, 2011·Journal of the American Chemical Society·James M Camara, Thomas B Rauchfuss
Jun 19, 2012·Chemical Reviews·David R WeinbergThomas J Meyer
Oct 20, 2012·Dalton Transactions : an International Journal of Inorganic Chemistry·Shunichi Fukuzumi, Tomoyoshi Suenobu
Feb 14, 2013·Accounts of Chemical Research·Oliver S Wenger
Apr 3, 2013·Journal of the American Chemical Society·Takeshi MatsumotoMasako Kato
Aug 21, 2013·Accounts of Chemical Research·Markus D KärkäsBjörn Akermark
Sep 6, 2013·Inorganic Chemistry·Tetsuro TanoShinobu Itoh
Dec 11, 2013·Journal of the American Chemical Society·Manuela A GrossErwin Reisner

❮ Previous
Next ❯

Methods Mentioned

BETA
phosphorescence
dynamic light scattering
NMR
irradiated

Software Mentioned

VESTA
Gaussian
GaussSum

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.