866613-66-3Relevant academic research and scientific papers
Ni, Pd, and Pt complexes of a tetradentate dianionic thiosemicarbazone-based O^N^N^S ligand
Haseloer, Alexander,Denkler, Luca Mareen,Jordan, Rose,Reimer, Max,Olthof, Selina,Schmidt, Ines,Meerholz, Klaus,H?rner, Gerald,Klein, Axel
, p. 4311 - 4322 (2021/04/06)
New tetradentate phenolate O^N^N^S thiosemicarbazone (TSC) ligands and their Ni(ii), Pd(ii) and Pt(ii) complexes were studied. The diamagnetic and square planar configured orange or red complexes show reversible reductive electrochemistry and in part reversible oxidative electrochemistry at very moderate potentials. DFT calculations show essentially pyridyl-imine centred lowest unoccupied molecular orbitals (LUMO) while the highest occupied molecular orbitals (HOMO) receive contributions from the phenolate moiety, the metal d orbitals and the TSC thiolate atom in keeping with UV-vis spectroelectrochemistry. DFT calculations in conjunction with IR spectra showed details of the molecular structures, the UV-vis absorptions were modelled through TD-DFT calculation with very high accuracy. UPS is fully consistent with UV-vis absorption and TD-DFT calculated data and shows decreasing HOMO-LUMO gaps along the series Pd > Pt > Ni.
Convenient and rapid strategies towards 6-(hetero)aryl pyridylmethylamines: First catalytic issues
Requet, Alexandre,Yalgin, Hasret,Prim, Damien
supporting information, p. 1378 - 1382 (2015/03/04)
The convenient preparation of new pyridylmethylamines is described using a short two step sequence. The first step involved the straightforward microwave-assisted construction of 6-aryl and 6-heteroaryl pyridine scaffolds bearing carboxaldehyde and nitrile fragments. The pendant arm comprising a second nitrogen atom by mean of amine and oxazoline moieties is installed in the second step. Finally, a first entry towards catalytic activity is given. In this context, modification of the ligand pattern and steric crowding around the central pyridine ring is examined and led to modest to fair ee's in the construction of binaphthyl substrates.
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.
