Helpful correlations to estimate the pK of coordinated HNO: a potential-pH exploration in a pendant-arm cyclam-based ruthenium nitroxyl.

The acid-base speciation of coordinated azanone (HNO) remains a highly relevant topic in bioinorganic chemistry. Ruthenium nitroxyl complexes with sufficient robustness towards ligand loss have gained significance as operating platforms to delve into such studies. In this work, we revisit an octahedral {RuNO} complex containing the cyclam-based pentadentate ligand L = 1-(pyridine-2-ylmethyl)-1,4,8,11-tetraazacyclotetradecane and explore the thermodynamic and spectroscopic aspects of its reduced states in aqueous media.

Chlorido(4,4'-dimethoxy-2,2'-bipyridine)(1,4,7-trimethyl-1,4,7-triazacyclononane)ruthenium(II) perchlorate acetonitrile disolvate and aqua(4,4'-dimethoxy-2,2'-bipyridine)(1,4,7-trimethyl-1,4,7-triazacyclononane)ruthenium(II) bis(perchlorate) dihydrate.

The title complexes, [RuCl(C(9)H(21)N(3))(C(12)H(12)N(2)O(2))]ClO(4)·2C(2)H(3)N, (I), and [Ru(C(9)H(21)N(3))(C(12)H(12)N(2)O(2))(H(2)O)](ClO(4))(2)·2H(2)O, (II), display similar structures with the Ru atom in a distorted octahedral environment. In the crystal packing of the chloride complex, (I), the Ru complex molecules are held together in pairs through C-H···Cl interactions of the 4,4'-dimethoxy-2,2'-bipyridine and chloride ligands. In the case of the aqua complex, (II), hydrogen bonding affords a tetrameric hydrogen-bonded network.

Four Ni(II) complexes with the new cyclam-methylimidazole ligand 1-[(1-methyl-1H-imidazol-2-yl)methyl]-1,4,8,11-tetraazacyclotetradecane.

Although it has not proved possible to crystallize the newly prepared cyclam-methylimidazole ligand 1-[(1-methyl-1H-imidazol-2-yl)methyl]-1,4,8,11-tetraazacyclotetradecane (L(Im1)), the trans and cis isomers of an Ni(II) complex, namely trans-aqua{1-[(1-methyl-1H-imidazol-2-yl)methyl]-1,4,8,11-tetraazacyclotetradecane}nickel(II) bis(perchlorate) monohydrate, [Ni(C(15)H(30)N(6))(H(2)O)](ClO(4))(2)·H(2)O, (1), and cis-aqua{1-[(1-methyl-1H-imidazol-2-yl)methyl]-1,4,8,11-tetraazacyclotetradecane}nickel(II) bis(perchlorate), [Ni(C(15)H(30)N(6))(H(2)O)](ClO(4))(2), (2), have been prepared and structurally characterized. At different stages of the crystallization and thermal treatment from which (1) and (2) were obtained, a further two compounds were isolated in crystalline form and their structures also analysed, namely trans-{1-[(1-methyl-1H-imidazol-2-yl)methyl]-1,4,8,11-tetraazacyclotetradecane}(perchlorato)nickel(II) perchlorate, [Ni(ClO(4))(C(15)H(30)N(6))]ClO(4), (3), and cis-{1,8-bis[(1-methyl-1H-imidazol-2-yl)methyl]-1,4,8,11-tetraazacyclotetradecane}nickel(II) bis(perchlorate) 0.24-hydrate, [Ni(C(20)H(36)N(6))](ClO(4))(2)·0.

Probing the chemotaxis periplasmic sensor domains from Geobacter sulfurreducens by combined resonance Raman and molecular dynamic approaches: NO and CO sensing.

The periplasmic sensor domains encoded by genes gsu0582 and gsu0935 are part of methyl accepting chemotaxis proteins in the bacterium Geobacter sulfurreducens (Gs). The sensor domains of these proteins contain a heme-c prosthetic group and a PAS-like fold as revealed by their crystal structures. Biophysical studies of the two domains showed that nitric oxide (NO) binds to the heme in both the ferric and ferrous forms, whereas carbon monoxide (CO) binds only to the reduced form.

Widely differing photochemical behavior in related octahedral {Ru-NO}6 compounds: intramolecular redox isomerism of the excited state controlling the photodelivery of NO.

trans-[(NC)Ru(py)(4)(mu-CN)Ru(py)(4)(NO)](3+) (py = pyridine) is a stable species in aqueous solution. It displays an intense absorption in the visible region of the spectrum (lambda(max) = 518 nm; epsilon(max) = 6100 M(-1) cm(-1)), which turns this compound into a promising agent for the photodelivery of NO. The quantum yield for the photodelivery process resulting from irradiation with 455 nm visible light was found experimentally to be (0.

All-trans-[ClRu(II)(py)4(NC)Ru(II)(py)4(CN)Ru(II)(py)4(NO)](PF6)4: a redox-active 2-donor/1-acceptor system based on the electrophilic {RuNO}6 motif.

The new linear homotrinuclear compound trans-[ClRu(II)(py)(4)(NC)Ru(II)(py)(4)(CN)Ru(II)(py)(4)(NO)](PF(6))(4) was prepared by reaction between the nitro complex trans-[(NC)Ru(II)(py)(4)(CN)Ru(II)(py)(4)(NO(2))](+) and the solvento complex obtained by reaction between [ClRu(II)(py)(4)(NO)](3+) and N(3)(-) in acetone. The trans-[ClRu(II)(py)(4) (NC)Ru(II)(py)(4)(CN)Ru(II)(py)(4)(NO)](4+) ion (I) has been characterized by (1)H NMR and IR spectroscopy (nu(NO) = 1919 cm(-1)). This species displays intense electronic absorptions in the visible region which can be assigned to donor-acceptor charge-transfer transitions (DACT) involving {RuNO}(6)-centered acceptor orbitals and donor orbitals located on the two different neighboring metal centers at ca.