Refernces
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.
10.1002/anie.201807642
The research investigates the enhanced solubility of halide-containing organometallics in diiodomethane (CH2I2) compared to other haloalkane solvents. The study hypothesizes that the solvent's complex halogen bonding is responsible for the improved solubility. Experiments involved preparing and characterizing a series of palladium and platinum isocyanide complexes using techniques like CHN elemental analysis, high-resolution mass spectrometry, FT-IR, and NMR spectroscopy. Solubility was measured using quantitative 1H NMR spectroscopy with hexamethyldisiloxane as an internal standard. The researchers also calculated the electrostatic potential of the s-holes (VS(r)max) in the solvents to assess their halogen bonding ability. The results showed that CH2I2 had the highest solubility for the organometallic model compounds, suggesting that its strong s-hole donating ability leads to uniquely strong solvent-(metal complex) halogen bonding, which was further supported by crystal structure analyses and quantum chemical calculations.
10.1016/S0040-4039(00)87522-X
The research explores a method for the methylidenation and ethylidenation of allylic thioethers, leading to a 2,3-sigmatropic rearrangement. The study aims to convert allylic phenylthioethers into homoallylic phenylthioethers in a single step using methylene iodide or ethylidene iodide in the presence of diethylzinc, bypassing the need for the Simmons-Smith reaction, which was found to be ineffective in the presence of thioethers. The researchers discovered that the use of diethylzinc and methylene iodide in a homogeneous solution successfully executed the desired transformation, avoiding the formation of an insoluble polymer that occurred with zinc-copper or zinc-silver couples. Key chemicals used in this process include methylene iodide, ethylidene iodide, diethylzinc, and various thioethers such as allylic phenyl sulfide and dimethyl sulfide. The study concluded that the rearrangement could be initiated by ethylidene iodide but not by other diiodoalkanes, and the procedure was effective for the selenium analogue as well, demonstrating the versatility of the method in organic synthesis.
Xi
Xi:Irritant;
