A Hemilabile and Cooperative N-Donor-Functionalized 1,2,3-Triazol-5-Ylidene Ligand for Alkyne Hydrothiolation Reactions
CHEMISTRY-A EUROPEAN JOURNAL
Authors: Strydom, Ian; Guisado-Barrios, Gregorio; Fernandez, Israel; Liles, David C.; Peris, Eduardo; Bezuidenhout, Daniela I.
Abstract
A series of novel cationic and neutral Rh complexes with an N-donor-functionalized 1,2,3-triazol-5-ylidene (TRZ) ligand (in which the pendant N donor is NHBoc, NH2, or NMe2) is described. The catalytic activity of these complexes was evaluated in the hydrothiolation of alkynes. Among the catalysts, a neutral dicarbonyl complex featuring the tethered-NBoc amido-TRZ ligand proved very selective for alkyne hydrothiolation with an aryl thiol. Remarkably, the reaction could be carried out in the absence of pyridine or base additive. In addition, during the reaction, no evidence for oxidative addition of the thiol S-H bond was observed, strongly suggesting a reaction pathway in which a bifunctional ligand is involved. Experimental and theoretical mechanistic investigations suggest a ligand-assisted deprotonation of thiol, hemilabile dissociation of amine from the metal, and thiolate coordination, which is indicative of a different reaction mechanism to those previously reported for related alkyne hydrothiolation reactions.
Synthesis and Characterization of Nonclassical Interhalides Based on Bromine Monochloride
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
Authors: Schmidt, Benjamin; Sonnenberg, Karsten; Beckers, Helmut; Steinhauer, Simon; Riedel, Sebastian
Abstract
Due to a more distinct sigma-hole, BrCl is able to form stronger halogen bonds than those in polyhalogen anions based on Cl-2 and Br-2. This stabilization allows the crystallographic characterization of a variety of new polyinterhalides, in which chloride functions as the central ion as shown by the molecular structures of [AsPh4][Cl(BrCl)(3)] and [CCl(NMe2)(2)][Cl(BrCl)(5)]. Furthermore, the solid-state structure of an octahedrally coordinated nonclassical interhalide is reported for the first time. The tridecainterhalide monoanion [Cl(BrCl)(6)](-) consists of a central chloride ion, which is coordinated by six BrCl molecules in a slightly distorted octahedral structure. All new compounds were characterized by single-crystal X-ray diffraction (XRD), NMR and Raman spectroscopy, as well as quantum-chemical calculations.