Discrete Singular Metallophilic Interaction in Stable Large 12-Membered Binuclear Silver and Gold Metallamacrocycles of Amido-Functionalized Imidazole and 1,2,4-Triazole-Derived N-Heterocyclic Carbenes.

Metallophilic interactions were observed in four pairs of 12-membered metallamacrocyclic silver and gold complexes of imidazole-derived N-heterocyclic carbenes (NHCs), [1-(R1)-3-N-(2,6-di-(R2)-phenylacetamido)-imidazol-2-ylidene]2M2 [R1 = p-MeC6H4, R2 = Me, M = Ag (1b) and Au (1c); R1 = Me, R2 = i-Pr, M = Ag (2b) and Au (2c); R1 = Et, R2 = i-Pr, M = Ag (3b) and Au (3c)], and a 1,2,4-triazole-derived N-heterocyclic carbene (NHC), [1-(i-Pr)-4-N-(2,6-di-(i-Pr)-phenylacetamido)-1,2,4-triazol-2-ylidene]2M2 [M = Ag (4b) and Au (4c)]. The X-ray diffraction, photoluminescence, and computational studies indicate the presence of metallophilic interactions in these complexes, which are significantly influenced by the sterics and the electronics of the N-amido substituents of the NHC ligands. The argentophilic interaction in the silver 1b-4b complexes was stronger than the aurophilic interaction in the gold 1c-4c complexes, with the metallophilic interaction decreasing in the order 4b > 1b > 1c > 4c > 3b > 3c > 2b > 2c. The 1b-4b complexes were synthesized from the corresponding amido-functionalized imidazolium chloride 1a-3a and the 1,2,4-triazolium chloride 4a salts upon treatment with Ag2O. The reaction of 1b-4b complexes with (Me2S)AuCl gave the gold 1c-4c complexes.

One pot tandem dehydrogenative cross-coupling of primary and secondary alcohols by ruthenium amido-functionalized 1,2,4-triazole derived N-heterocyclic carbene complexes.

One-pot tandem dehydrogenative cross-coupling of primary and secondary alcohols was catalyzed by three ruthenium complexes [1-(R)-4-N-(furan-2-ylmethyl)acetamido-1,2,4-triazol-5-ylidene]Ru(p-cymene)Cl [R = Et (1b), i-Pr (2b), Bn (3b)], of amido-functionalized 1,2,4-triazole derived N-heterocyclic carbene (NHC) ligands. Density Functional Theory (DFT) calculations were employed for the ruthenium (1b) precatalyst to understand this reaction mechanism completely, and the mechanisms adapted are divided categorically into three steps (i) nucleophilic substitution of chloride ions by alcohols, (ii) dehydrogenation of primary and secondary alcohols, and (iii) olefin and ketone hydrogenation. Our mechanistic study reveals that the formation of a deprotonated Ru-alcoholate (A) or (E) intermediate is favorable compared to the protonated form (A') or (E') from (1b) by associative nucleophilic substitution. Though an ionic pathway that proceeds through (A') or (E'), has less barriers in the dehydrogenation and olefin/ketone hydrogenation steps than that of the neutral pathway, proceeding through (A) or (E), a steep energy barrier was observed in the first nucleophilic substitution step, prohibiting the reaction to proceed via the intermediate (A') or (E'). Thus, our thorough mechanistic study reveals that the reaction proceeds via deprotonated Ru-alcoholate (A) or (E) species. Furthermore, the 1,4 addition of an α,ß-unsaturated carbonyl compound is kinetically and thermodynamically favorable over the 1,2 addition, and the experiments support these observations. As a testimony towards practical application in synthesizing bio-active flavonoid based natural products, five different flavan derivatives (16-20), were synthesized by the dehydrogenative coupling reaction using the neutral ruthenium (1-3)b complexes.