10.1021/acs.inorgchem.9b03065
The research focuses on the diverse functionalization of ruthenium-chelated 2-picolylamines (PA), exploring reactions such as oxygenation, dehydrogenation, cyclization, and N-dealkylation. The experiments involve the reaction of metal precursor [RuII(Cl)(H)(CO)(PPh3)3] with PA derivatives under basic conditions, leading to the formation of various products based on the tuning of amine nitrogen (Namine) and methylene center (Cα) at the PA backbone. Reactants include PA derivatives with different substituents at Namine and Cα positions, as well as external electrophiles like benzyl bromide and methylene iodide. The analyses used to characterize the products and reaction pathways encompass crystal structures, spectroscopic features (1H/13C/31P NMR, UV-vis, and IR), electrospray ionization mass spectrometry (ESI-MS), gas chromatography-mass spectrometry (GC-MS), and theoretical calculations using density functional theory (DFT). These methods collectively authenticate the product formation and elucidate the reaction mechanisms, highlighting the "chemical noninnocence" of PA derivatives in ruthenium complexes.
10.1007/s11172-008-0126-4
The research focuses on the synthesis and application of pyrrolidine and pyrroline derivatives of fullerenes C60 and C70 through [2+3] cycloaddition reactions using azomethine and nitrile ylides generated from picolylamine and benzylamine derivatives. The study explores the use of catalysts and microwave radiation to enhance the formation of ylides and their addition to fullerenes, resulting in higher yields (80-85%) compared to the classical Prato reaction. The synthesized compounds exhibit high regio- and stereoselectivity, forming cis-2′,5′-disubstituted and trans-1′,2′,5′-trisubstituted pyrrolidinofullerenes. These derivatives are of interest for their potential use in light-converting systems, such as solar cells, due to their ability to form self-ordered coordination complexes with metalloporphyrins and phthalocyanines, which can mimic natural photosynthetic antenna systems through photoinduced charge separation. The research also highlights the development of efficient methods for synthesizing these derivatives on a macroscale, addressing challenges related to scalability, energy consumption, and product separation.
10.1016/j.tet.2009.04.031
The research focuses on the synthesis and study of flexible amide ligands for metallo-supramolecular assemblies aimed at anion binding. The researchers synthesized seven flexible bidentate bis-pyridyl diamide and four monodentate pyridyl amide ligands containing central amide units. These ligands possess external metal coordinating pyridyl groups and internal amide functionalities, with the potential to bind anions. The bis-pyridyl ligands were prepared in one step from commercially available compounds, yielding moderate to good results. The study includes the crystal structures of six of the bis-pyridyl diamide ligands, revealing various hydrogen bonding networks and conformations. The chemicals that played a significant role in this research include nicotinoyl and iso-nicotinoyl chlorides, various diamines, phthaloyl chloride, 2,6-dimethylpyridine dicarboxylate, and different aminomethylpyridines. These compounds were used to create the ligands and study their properties in the context of metallo-supramolecular assemblies for anion binding.
10.1021/ol301635x
The research aims to develop a method for the ortho C—H borylation of benzylic amines using an iridium catalyst. Typically, C—H borylation reactions are governed by steric effects, leading to meta- and para-functionalization of arenes. This study seeks to reverse this inherent selectivity to achieve ortho borylation, thereby expanding the range of accessible arylboronate esters. The key chemicals involved include the iridium catalyst [Ir(μ-OMe)(COD)]2, picolylamine as the ligand, and various benzylic amine substrates. The researchers discovered that picolylamine effectively induces the directing effect necessary for ortho borylation, replacing the commonly used 4,4'-di-tert-butylbipyridine. Through optimization, they achieved high conversion rates and selectivity for mono ortho borylation products. The directing effect is proposed to result from the partial dissociation of one amine nitrogen of the picolylamine ligand, rather than hydrogen bonding as initially hypothesized. The study concludes that this method provides good yields and selectivity for mono ortho borylation products when using basic amines, significantly advancing the field of C—H borylation.
10.1002/1099-0682(200103)2001:3<805::AID-EJIC805>3.0.CO;2-2
The study focuses on the synthesis and properties of dimetallic complexes based on a new oxalamidine-derived ligand system with pendant pyridine functionality. The researchers used sterically hindered bis(imidoyl)chlorides of oxalic acid and picolylamine to create conformationally locked oxalic acid-derived amidines with pendant pyridine functional groups. These amidines served as multivalent ligands for the formation of heterodimetallic and homodimetallic diazadiene complexes, which are of interest due to their potential cooperative effects in catalysis, intramolecular electron transfer reactions, and magnetic interactions. The study also explores the coordination chemistry of these ligands with various metals, including molybdenum, cobalt, and copper, to understand their conformational restrictions and the role of intramolecular hydrogen bonding in their structure and reactivity. The synthesized complexes were characterized using various analytical techniques, including NMR, IR, and X-ray crystallography.
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