A chiral iron-sexipyridine complex-hydrogen peroxide mixture is a highly efficient catalytic system for styrene epoxidation with excellent reactivity (3 min, 95% yield) and chemoselectivity (98%).
New binuclear double-stranded helicates were formed between manganese(ii) perchlorate and chiral phenyl- and polyphenyl-bridged oligopyridines; they are active catalysts for alkene epoxidation.
Two series of chiral helical copper–quaterpyridine complexes were prepared by reacting chiral ligands L1–4 with CuI and CuII precursors. The CuII complexes, [Cu(L)(H2O)(ClO4)2] or [Cu(L)(ClO4)2], were studied by ESI‐MS, elemental analysis, and CD spectroscopy, and the CuI complexes, [Cu2(L)2](PF6)2, were examined by NMR, ESI‐MS, elemental analysis, and CD spectroscopy. The crystal structures of [Cu(L1)(H2O)(ClO4)](ClO4) and [Cu(L3)(ClO4)2] were determined by X‐ray diffraction. They are monomeric, distorted octahedral complexes with the quaterpyridine ligand coordinated at the four equatorial positions and one or two perchlorates at the apical position. The crystal structure of [Cu(L1m)(H2O)(ClO4)](ClO4), which has an achiral quaterpyridine ligand L1m, the meso form of L1, was also determined. Comparison between [Cu(L1)(H2O)(ClO4)](ClO4) and [Cu(L1m)(H2O)(ClO4)](ClO4) shows small differences between the two structures. CD analyses of mononuclear CuII complexes of sterically demanding L2–4 indicate that these structures require a helical twist in the ligand. The crystal structure of [Cu2(L3)2](PF6)2 shows that it is a two‐metal two‐ligand double‐stranded helical structure. Solution NMR studies of the dinuclear CuI complexes show that each sample consists of two diastereomers with moderate to high diastereoselectivity (52–99 %). With L1m, head‐to‐head and head‐to‐tail configurational isomers were formed in an almost 1:1 ratio. Heterostranded helicates could also be formed with two different chiral ligands but selectivity favors the homostranded one. DFT calculations on the homostranded helicates yield evidence that interactions between the chiral groups of the ligand strands in the helicate are not solely responsible for determining the helical chirality of the CuI complexes.
scite is a Brooklyn-based organization that helps researchers better discover and understand research articles through Smart Citations–citations that display the context of the citation and describe whether the article provides supporting or contrasting evidence. scite is used by students and researchers from around the world and is funded in part by the National Science Foundation and the National Institute on Drug Abuse of the National Institutes of Health.