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The work being reported here deals with the design of a new type of "N-H" Ni(II) complexes of glycine Schiff bases and study general aspects of their reactivity. It was confirmed that the presence of NH function in these Ni(II) complexes does not interfere with the homologation of the glycine residue, rendering these derivatives of high synthetic value for the general synthesis of α-amino acids. In particular, the practical application of these NH-type complexes was demonstrated by asymmetric synthesis of various β-substituted pyroglutamic acids via Michael addition reactions with chiral Michael acceptors.
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http://dx.doi.org/10.1039/c3ob41959b | DOI Listing |
Chemistry
December 2024
University of Münster Department of Chemistry and Pharmacy: Westfalische Wilhelms-Universitat Munster Fachbereich 12 Chemie und Pharmazie, Institut für Anorganische und Analytische Chemie, Corrensstr. 28/30, 48149, Münster, GERMANY.
Two artificial imidazole-derived nucleobases, HQIm (3H-imidazo[4,5-f]quinolin-5-ol) and CaIm (imidazole-4-carboxylate), were introduced into short DNA duplexes to systematically investigate their thermal stability upon metal ion coordination. Metal-mediated base pairs are formed with the 3d metal ions CoII, NiII and ZnII, as well as with the lanthanoid ions EuIII and SmIII, which induce a thermal stabilization of up to 8 °C upon binding. The latter are the first lanthanoid-mediated base pairs involving only four donor atoms that result in a significant duplex stabilization.
View Article and Find Full Text PDFBiometals
December 2024
Department of Chemistry, Baba Mastnath University, Asthal Bohar, Rohtak, 124021, India.
The Schiff base metal complexes containing the transition metal ions Co(II), Ni(II) and Cu(II) were synthesized using their nitrate and acetate salts. An octahedral environment encircling metal complexes has been demonstrated by the findings of multiple spectroscopic approaches that were employed to demonstrate the structure of the metal complexes. The Coats-Redfern method of thermal analysis was employed to carry out the kinetic and thermodynamic calculations.
View Article and Find Full Text PDFActa Crystallogr E Crystallogr Commun
October 2024
Department of Chemistry, Taras Shevchenko National University of Kyiv, Volodymyrska Street 64, Kyiv, 01601, Ukraine.
The unit cell of the title compound, [Ni(CHClN)]·2CHOH, consists of a neutral complex and two methanol mol-ecules. In the complex, the two tridentate 2-(3-(4-chloro-phen-yl)-1-1,2,4-triazol-5-yl)-6-(1-pyrazol-1-yl)pyridine ligands coordinate to the central Ni ion through the N atoms of the pyrazole, pyridine and triazole groups, forming a pseudo-octa-hedral coordination sphere. Neighbouring tapered mol-ecules are linked through weak C-H(pz)⋯π(ph) inter-actions into monoperiodic chains, which are further linked through weak C-H⋯N/C inter-actions into diperiodic layers.
View Article and Find Full Text PDFJ Phys Chem Lett
December 2024
Stanford PULSE Institute, SLAC National Accelerator Laboratory, Stanford University, Menlo Park, California 94025, United States.
Ni 2,2'-bipyridine complexes are commonly invoked intermediates in metallaphotoredox cross-coupling reactions. Despite their ubiquity, design principles targeting improved catalytic performance remain underdetermined. A series of Ni(bpy)(Ar)Cl (R = MeOOC, -Bu, R' = CH, CF) complexes were proposed to have multiconfigurational electronic structures on the basis of multiconfigurational/multireference calculations, with significant mixing of Ni → bpy metal-to-ligand charge transfer (MLCT) configurations into the ground-state wave function.
View Article and Find Full Text PDFJ Org Chem
December 2024
Department of Crystallography, Institute of Chemistry, University of Silesia, 40-006 Katowice, Poland.
A facile, cost-effective, and sustainable synthesis of substituted triazines from primary alcohols by newly synthesized nickel pincer-type complexes (-) has been described. Herein, we report the synthesis of a set of three well-defined Ni(II) O^N^O pincer-type complexes, structurally characterized by analytical, spectral, and X-ray diffraction techniques. Further, the nickel complexes are explored as efficient catalysts (4 mol %) for the construction of 2,4,6-substituted 1,3,5-triazines from readily available alcohols via an acceptorless dehydrogenative coupling (ADC) strategy.
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