The synthesis, structure, reactivity and electrochemical properties of ruthenium complexes featuring cyanoacetylide ligands

The complex [Ru(C&3bond; CC&3bond; N)(dppe)Cp*] (1) is readily obtained (ca. 70%) from the sequential reaction of [Ru(C=CH2)(dppe)Cp*]PF6 with (BuLi)-Bu-n and phenyl cyanate. The complex behaves as a typical transition metal acetylide upon reaction with tetracyanoethene, affording a metallated pentacyanobutadiene. Complex I is a useful metalloligand, and its reactions with [W(thf)(CO)5], [RuCl(PPh3)(2)Cp], [RuCl(dppe)Cp*] or cis-[RuCl2(dppe)(2)] all afforded products featuring the M-C&3bond; CC&3bond; N-M' motif, for which ground state structures indicate a degree of polarisation. Electrochemical and spectroelectrochemical studies reveal moderate interactions between the metal centres in the 35-electron dications [{Cp*(dppe)Ru}(mu-C&3bond; CC&3bond; N){RuL2Cp'}](2+) Ru(PPh3)(2)CP, Ru(dppe)Cp*).

Synthesis and characterization of Cu(II) complexes of tetradentate and tridentate symmetrical Schiff base ligands involving o-phenelenediamine, salicylaldehyde and diacetylmonoxime

A mononuclear complex [CuL] (1), a binuclear complex [Cu2LCl2(H2O)] (2), a trinuclear complex [Cu3L2](ClO4)(2) (3) involving o-phenylenediamine and salicylaldehyde and another binuclear complex of a tridentate ligand (H2L1) [Cu2L (2) (1) ](CH3COO)(2) (4) involving o-phenylenediamine and diacetylmonoxime have been synthesized, where H2L = N,N'-o-phenylenebis(salicylideneimine) and H2L1 = 3-(2-aminophenylimino)butan-2-one oxime. All the complexes have been characterized by elemental analyses, spectral and magnetic studies. The binuclear complex (2) was characterized structurally where the two Cu(II) centers are connected via an oxygen-bridged arrangement.

Segregated self-assembly and pillaring action of aliphatic dicarboxylic acids in the super structure of Cu-picolinate complexes

Three new supramolecular assemblies of co-crystallized metal complexes and aliphatic dicarboxylic acids, {[Cu(pic)(2)(H2O)(2)](H(2)mal)}(n) (1), {[Cu(pic)(2)(H2O)(2)](H(2)mal)(2)(H2O)(2)}(n) (2) and {[Cu(pic)(2)(MeOH)](H(2)succ)}(n) (3) {Hpic = 2-picolinic acid, H(2)mal = malonic acid and H(2)succ = succinic acid} have been synthesized and characterized by X-ray single-crystal structure determination. The crystal packings of the complexes reveal that supramolecular associations of the monomeric complex units lead to the formation of layers through hydrogen bonding. In all the complexes, the dicarboxylic acid units connect the 2-D layers to act as pillars. The interaction between water molecules and the dicarboxylic acid plays an important role in the overall supramolecular assembly. (C) 2008 Elsevier Ltd. All rights reserved.

Effects of high pressure/thermal treatment on lipid oxidation in beef and chicken muscle

Lipid oxidation was studied in beef and chicken muscle after high pressure treatment (0.1-800 MPa) at different temperatures (20-70 degrees C for 20 min, prior to storage at 4 degrees C for 7 days. Pressure treatment of beef samples at room temperature led to increases in TBARS values after 7 days storage at 4 degrees C; however, the increases were more marked after treatment at pressures >= 400 MPa (at least fivefold) than after treatment at lower pressures (less than threefold). Similar results were found in those samples treated at 40 degrees C, but at 60 degrees C and 70 degrees C pressure had little additional effect on the oxidative stability of the muscle. Pressure treatments of 600 MPa and 800 MPa, at all temperatures. induced increased rates of lipid oxidation in chicken muscle, but, in general, chicken muscle was more stable than beef to pressure. and the catalytic effect of pressure was still seen at the higher temperatures of 50 degrees C, 60 degrees C and 70 degrees C. The addition of 1%, Na(2)EDTA decreased TBARS values of the beef muscle during storage and inhibited the increased rates of lipid oxidation induced by pressure. The inhibition by vitamin E (0.05% w/w) and BHT (0.02% w/w), either alone or in combination, were less marked than seen with Na(2)EDTA, suggesting that transition metal ions released from insoluble complexes are of major importance in catalysing lipid oxidation in pressure-treated muscle foods. (c) 2007 Elsevier Ltd. All rights reserved.

Photochromic dithienylethene derivatives containing Ru(II) or Os(II) metal units. Sensitized photocyclization from a triplet state

Efficient photocyclization from a low-lying triplet state is reported for a photochromic dithienylperfluorocyclopentene with Ru(bpy)(3) units attached via a phenylene linker to the thiophene rings. The ring-closure reaction in the nanosecond domain is sensitized by the metal complexes. Upon photoexcitation into the lowest Ru-to-bpy (MLCT)-M-1 state followed by intersystem crossing to emitting (MLCT)-M-3 states, photoreactive (IL)-I-3 states are populated by an efficient energy-transfer process. The involvement of these (IL)-I-3 states explains the quantum yield of the photocyclization, which is independent of the excitation wavelength but decreases strongly in the presence of dioxygen. This behavior differs substantially from the photocyclization of the nonemissive dithienylperfluorocyclopentene free ligand, which occurs from the lowest (IL)-I-1 state on a picosecond time scale and is insensitive to oxygen quenching. Cyclic voltammetric studies have also been performed to gain further insight into the energetics of the system. The very high photocyclization quantum yields, far above 0.5 in both cases, are ascribed to the strong steric repulsion between the bulky substituents on the dithienylperfluorocyclopentene bridge bearing the chelating bipyridine sites or the Ru(bpy)(3) moieties, forcing the system to adopt nearly exclusively the reactive antiparallel conformation. In contrast, replacement of both Ru(II) centers by Os(II) completely prevents the photocyclization reaction upon light excitation into the low-lying Os-to-bpy (MLCT)-M-1 state. The photoreaction can only be triggered by optical population of the higher lying (IL)-I-1 excited state of the central photochromic unit, but its yield is low due to efficient energy transfer to the luminescent lowest (MLCT)-M-3 state.

Multimetallic ruthenium(II) complexes as electrochemiluminescent labels

Two homometallic complexes containing two and three ruthenium polypyridyl units linked by amino acid lysine (Lys) and the related dipeptide (LysLys) were synthesized and their electrochemical, spectroscopic, and electrochemiluminescence (ECL) properties were investigated. The electrochemical and photophysical data indicate that the two metal complexes largely retain the electronic properties of the reference compound for the separate ruthenium moieties in the two bridged complexes, [4-carboxypropyl-4'-methyl-2,2'-bipyridine]bis(2,2'-bipyridine)ruthenium(II) complex. The ECL studies, performed in aqueous media in the presence of tri-n-propylamine as co-reactant, show that the ECL intensity increases by 30% for the dinuclear and trinuclear complexes compared to the reference. Heterogeneous ECL immunoassay studies, performed on larger dendritic complexes containing up to eight ruthenium units, demonstrate that limitations due to the slow diffusion can easily be overcome by means of nanoparticle technology. In this case, the ECL signal is proportional to the number of ruthenium units. Multimetallic systems with several ruthenium centers may, however, undergo nonspecific bonding,to streptavidin-coated particles or to antibodies, thereby increasing the background ECL intensity and lowering the sensitivity of the immunoassay.

Structure and magnetic properties of an unprecedented syn-antiμ-nitrito-1κO:2κO′ bridged Mn(iii)-salen complex and its isoelectronic and isostructural formate analogue

The preparation, crystal structures and magnetic properties of two new isoelectronic and isomorphous formate-and nitrite-bridged 1D chains of Mn(III)-salen complexes, [Mn(salen)(HCOO)](n) (1) and [Mn(salen)(NO2)](n) (2), where salen is the dianion of N,N'-bis(salicylidene)-1,2-diaminoethane, are presented. The structures show that the salen ligand coordinates to the four equatorial sites of the metal ion and the formate or nitrite ions coordinate to the axial positions to bridge the Mn(III)-salen units through a syn-anti mu-1 kappa O:2 kappa O' coordination mode. Such a bridging mode is unprecedented in Mn(III) for formate and in any transition metal ion for nitrite. Variable-temperature magnetic susceptibility measurements of complexes 1 and 2 indicate the presence of ferromagnetic exchange interactions with J values of 0.0607 cm(-1) (for 1) and 0.0883 cm(-1) (for 2). The ac measurements indicate negligible frequency dependence for 1 whereas compound 2 exhibits a decrease of chi(ac)' and a concomitant increase of chi(ac)'' on elevating frequency around 2 K. This finding is an indication of slow magnetization reversal characteristic of single-chain magnets or spin-glasses. The mu-nitrito-1 kappa O:2 kappa O' bridge seems to be a potentially superior magnetic coupler to the formate bridge for the construction of single-molecule/-chain magnets as its coupling constant is greater and the chi(ac)' and chi(ac)'' show frequency dependence.

RuII(α-diimine) or RuIII(α-diimine·–)? Structural, spectroscopic, and theoretical evidence for the stabilization of a prominent metal-to-Ligand charge- transfer excited-state configuration in the ground state

The new compounds [Ru(R-DAB)(acac)2] (R-DAB = 1,4-diorganyl- 1,4-diazabuta-1,3-diene; R = tert-butyl, 4-methoxyphenyl, 2,6-dimethylphenyl; acac– = 2,4-pentanedionate) exhibit intrachelate ring bond lengths 1.297complexes and in view of other (α-diimine)- metal complexes with ambiguous oxidation-state assignments.