866613-54-9Relevant academic research and scientific papers
Multiple-Site Concerted Proton–Electron Transfer in a Manganese-Based Complete Functional Model for [FeFe]-Hydrogenase
Chen, Lin,He, Shuanglin,Huang, Fang,Li, Fei,Liu, T. Leo,Wang, Fang,Wu, Qianqian,Xiong, Ying,Yang, Jie,Zhang, Ping,Zhang, Rong
supporting information, p. 25839 - 25845 (2021/11/09)
The active site of [FeFe]-hydrogenase (H2ase) is preorganized with an amine (azadithiolate) as a proton relay and a [4Fe4S] subunit as an electron reservoir, which together lower the overpotential for proton reduction and hydrogen oxidation by multiple-site concerted proton–electron transfer (MS-CPET). Herein, we report a mononuclear manganese complex, fac-[Mn(CO)3(6-(2-hydroxyphenol)-2-pyridine-2-quinoline) Br] (1), as a rare model to fully mimic the functions of the H2ase. In 1, a redox-active bidentate ligand with a pendent phenol replicates the roles of the electron reservoir and the proton relay in the enzyme. Experimental and theoretical studies revealed two consecutive MS-CPET processes in the catalytic cycle, in each of which an electron stored in the reductive ligand and a proton at the proximal phenol moiety are transferred to the Mn center in a concerted way. By virtue of this mechanism, complex 1 exhibited a low overpotential comparable to that of natural enzyme in electrochemical hydrogen production using phenol as a proton source.
Phenolate substituent effects on ring-opening polymerization of ε-caprolactone by aluminum complexes bearing 2-(phenyl-2-olate)-6-(1- amidoalkyl)pyridine pincers
Alkarekshi, Wafaa,Armitage, Andrew P.,Boyron, Olivier,Davies, Christopher J.,Govere, Matifadza,Gregory, Andrew,Singh, Kuldip,Solan, Gregory A.
, p. 249 - 259 (2013/02/25)
Interaction of the 2-(phenyl-2-ol)-6-ketiminopyridines 2-(4′-R 1-C6H3-2′-OH)-6-{CMe=N(2″,6″- i-Pr2C6H3)}C5H3N (R 1 = H (L1a-H), But (L
Use of Suzuki cross-coupling as a route to 2-phenoxy-6-iminopyridines and chiral 2-phenoxy-6-(methanamino)pyridines
Davies, Christopher J.,Gregory, Andrew,Griffith, Phillip,Perkins, Tom,Singh, Kuldip,Solan, Gregory A.
, p. 9857 - 9864 (2008/12/23)
The anisyl boronic acids, 2-OMe-3-R2-5-R1-C6H2B(OH)2 (R1=R2=H (a); R1=H, R2=Ph (b); R1=Me, R2=H (c); R1=Cl, R2=H (d); R1=t-Bu, R2=H (e)), have been employed in Suzuki cross-coupling reactions with either 2-bromo-6-formylpyridine (I) or 2-bromo-6-acetylpyridine (II) generating, following a facile deprotection step, the 2-phenoxy-6-carbonylpyridines, 2-(2′-OH-3′-R2-5′-R1-C6H2)-6-(CH{double bond, long}O)C5H3N (R1=R2=H (1a); R1=Me, R2=H (1c); R1=Cl, R2=H (1d); R1=t-Bu, R2=H (1e)) and 2-(2′-OH-3′-R2-5′-R1-C6H2)-6-(CMe{double bond, long}O)C5H3N (R1=R2=H (2a); R1=H, R2=Ph (2b)). Condensation reactions of 1 and 2 with 2,6-diisopropylaniline proceed smoothly to give the 2-phenoxy-6-iminopyridines, 2-(2′-OH-3′-R2-5′-R1-C6H2)-6-{CH{double bond, long}N(2,6-i-Pr2C6H3)}C5H3N (R1=R2=H (3a); R1=Me, R2=H (3c); R1=Cl, R2=H (3d); R1=t-Bu, R2=H (3e)) and 2-(2′-OH-3′-R2-5′-R2-C6H2)-6-{CMe{double bond, long}N(2,6-i-Pr2C6H3)}C5H3N (R1=H, R2=Ph (4a), R1=H, R2=Ph (4b)). Reduction of the imino unit (and concomitant C-C bond formation) in 3 can be achieved by?treatment with trimethylaluminium or methyllithium which, following hydrolysis, furnishes the racemic chiral 2-phenoxy-6-(methanamino)pyridines, 2-(2′-OH-3′-R2-5′-R1-C6H2)-6-{CHMe-NH(2,6-i-Pr2C6H3)}C5H3N (R1=R2=H (5a); R1=Me, R2=H (5c); R1=Cl, R2=H (5d); R1=t-Bu, R2=H (5e)). This work represents a straightforward and rapid synthetic route to libraries of sterically and electronically variable phenoxy-substituted imino- and methanamino-pyridines, which are expected to act as useful ligands or proligands for late and early transition metal-mediated alkene polymerisation catalysis.
