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Exocyclic coordination chemistry of an O2S2- macrocycle with copper(i), mercury(ii) and palladium(ii) ions
The preparation and structures of the exocyclic coordination-based supramolecular complexes of a 14-membered dibenzo-O2S 2-macrocycle, L, with thiaphilic soft metal ions Cu(i), Hg(ii) and Pd(ii) are reported. The X-ray crystal structures of the eight complexes have been determined, and a range of the less common structural types, including mono- and multinuclear species with discrete and infinite forms were obtained. L reacts with copper(i) halides and afforded isostructural complexes of type [(Cu2X2)L]n (1: X = Cl, 2: X = Br) adopting a two-dimensional (2-D) polymeric structure linked by square-type Cu 2X2 clusters, while copper(i) iodide gave a yellow emissive complex {[(Cu4I4)L2]·2.5H 2O}n (3) whose crystal structure was not available. Treatment of L with copper(i) thiocyanate gave an infinite 2-D coordination network [CuLSCN]n (4) in which copper atoms are linked by SCN – forming a 1-D backbone, then further cross-linked by Lvia Cu-S bonds resulting in a grid-type layered structure. Reactions of L with HgX 2 (X = Br and I) resulted in the formation of an interesting “ivy-leaves” shaped complex [HgLBr2]n (5) with a syndiotactic arrangement and a single-stranded complex [(Hg2I 4)L]n (6), respectively, adopting an infinite 1-D structure. Unlike the copper(i) and mercury(ii) complexes with the infinite structures, reactions of L with Pd(NO3)2 gave a 1:1 (metal-to-ligand) dinitrato complex cis-[PdL(NO3)2] (7) and a 1:2 bis(macrocycle) complex cis-[PdL2](NO3) 2 (8) in a discrete form depending on the molar ratio of the reactants. A straightforward one-pot reaction of Pd(NO3)2 with two equivalents of L also resulted in the isolation of the bis(macrocycle) complex 8. The comparative NMR and ESI-mass studies for the palladium(ii) complexes were also carried out. The results are discussed in terms of the exo-coordination modes as well as the anion coordination.
The catalyzed pathway has a lower Ea, but the net change in energy that results from the reaction is not affected by the presence of a catalyst. In my other articles, you can also check out more blogs about 1111-67-7
Reference：
Copper catalysis in organic synthesis – NCBI,
Special Issue “Fundamentals and Applications of Copper-Based Catalysts”