Search

Ruthenium(II) π‐coordination onto [28]hexaphyrins(1.1.1.1.1.1) has been accomplished. Reactions of bis‐AuIII and mono‐AuIII complexes of hexakis(pentafluorophenyl) [28]hexaphyrin with [RuCl2(p‐cymene)]2 in the presence of NaOAc gave the corresponding π‐ruthenium complexes, in which the [(p‐cymene)Ru]II fragment sat on the deprotonated side pyrrole. A similar reaction of the bis‐PdII [26]hexaphyrin complex afforded a triple‐decker complex, in which the two [(p‐cymene)Ru]II fragments sat on both sides of the center of the [26]hexaphyrin framework. [ABSTRACT FROM AUTHOR]

We demonstrate here the synthesis of a novel class of metallo-supramolecular polymers with shackled structure, via the coordination of cyclic di(bisterpyridine-triphenyl ether ester) ligands with ruthenium-(II) ions. The constraint from the ring topology via the shackling of ligands provides novel properties to these metallo-supramolecular polymers, including the formation of dendritic crystals, red-shift of absorption bands in the UV--vis spectra from interchain charge-transfer transitions, and a typical flash-type memory behavior. [ABSTRACT FROM AUTHOR]

Ruthenium(II) polypyridyl complexes pro- mote the efficient radical cation Diels-Alder cycloaddition of electron-rich dienophiles upon irradiation with visible light. These reactions enable facile [4 + 2] cycloadditions that would be electronically mismatched under thermal conditions. Key to the success of this methodology is the availability of ligand-modified ruthenium complexes that enable rational tuning of the electrochemical properties of the catalyst without significantly perturbing the overall photophysical properties of the system. [ABSTRACT FROM AUTHOR]

The treatment of [Ru(LOEt)(N)Cl2] (1; LOEt- = [Co(η5-C5H5){P(O)(OEt)2}3]-) with Et3SiH affords [Ru(LOEt)Cl2(NH3)] (2), whereas that with [Ru(LOEt)(H)(CO)(PPh3)] (3) gives the dinuclear imido complex [(LOEt)Cl2Ru(μ-NH)Ru(CO)(PPh3)(LOEt)] (4). The imido group in 4 binds to the two ruthenium atoms unsymmetrically with Ru-N distances of 1.818(6) and 1.952(6) Å. The reaction between 1 and 3 at 25 °C in a toluene solution is first order in both complexes with a second-order rate constant determined to be (7.2 ± 0.4) × 10-5 M-1 s-1. [ABSTRACT FROM AUTHOR]

The article offers a description of a ruthenium/chiral diimino-diphosphine (PNNP)-catalyzed asymmetric Diels-Alder reaction. It notes that the PNNP complexes promote the enantioselective Diels-Alder reaction of α-methylene &#03B2;-keto esters to give tetrahydro-1-indanones. It explains that the diene attacks the open re enantioface of metal-bound dienophile in highly enantioselective fashion.