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Synthesis, structural, spectral, thermal and antimicrobial studies of palladium(II), platinum(II), ruthenium(III) and iridium(III) complexes derived from N,N,N,N-tetradentate macrocyclic ligand

Palladium(II), platinum(II), ruthenium(III) and iridium(III) complexes of general stoichiometry [PdL]Cl2, [PtL]Cl2, [Ru(L)Cl 2]Cl and [Ir(L)Cl2]Cl are synthesized with a tetradentate macrocyclic ligand, derived from 2,6-diaminopyridine with 3-ethyl 2,4-pentanedione. Ligand was characterized on the basis of elemental analyses, IR, mass, and 1H NMR and 13C NMR spectral studies. All the complexes were characterized by elemental analyses, molar conductance measurements, magnetic susceptibility measurements, IR, mass, electronic spectral techniques and thermal studies. The value of magnetic moments indicates that all the complexes are diamagnetic except Ru(III) complex which shows magnetic moments corresponding its one unpaired electron. The macrocyclic ligand and all its metal complexes were also evaluated in vitro against some plant pathogenic fungi and bacteria to assess their biocidal properties.

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Highly efficient and robust molecular ruthenium catalysts for water oxidation,
Catalysts | Special Issue : Ruthenium Catalysts – MDPI

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Coordination chemistry of and -, Y = S or Se, R = Ph or tBu: rhodium, iridium and ruthenium complexes; 13C, 31P, and 77Se NMR studies; and the crystal and molecular structures of >BF4*CHCl3 …

Reactions of the chloro-bridged complexes, , M = Ir or Rh, COD = cyclooctadiene, with CH2(PPh2)(P(Y)R2), Y = S or Se, R = Ph or t-Bu, provide a synthetic route to the cations, >+, which are isolated as fluoroborate or perchlorate salts.Treatment of these products with sodium hydride results in facile deprotonation to the neutral complexes, >, and when Y = S, the neutral complexes are also accessible via reactions of with Li.Reactions of the cations, >+ with other ligands, Lg = (CO)2, (CNt-Bu)2 or bis(diphenylphosphino)methane (dppm), result in displacement of cod to form >+.Ruthenium complexes of CH2(PPh2)(P(S)Ph2) are accessible via similar bridge cleavage reactions using , L = benzene or p-cymene.These complexes are characterized by complete 13C, 31P, and 77Se nuclear magnetic resonance (NMR) studies and by four crystal structure determinations.The complexes >BF4*CHCl3 (1), >ClO4*CH2Cl2 (2), > (3) and >*CH2Cl2 (4) crystallize in the P<*> (No. 2) space group (Z = 2) with respective unit cells: a = 12.307(7) Angstroem, b = 14.743(8) Angstroem, c = 10.877(6) Angstroem, alpha = 74.42(5) deg, beta = 107.65(6) deg, gamma = 105.47(5) deg; a = 12.163(1) Angstroem, b = 14.56(1) Angstroem, c = 10.560(1) Angstroem, alpha = 77.69(1) deg, beta = 74.54(1) deg, gamma = 77.01(1) deg; a = 10.650(4) Angstroem, b = 13.327(4) Angstroem, c = 10.419(3) Angstroem, alpha = 90.60(3) deg, beta = 102.64(3) deg, gamma = 83.15(3) deg; a = 11.217(2) Angstroem, b = 17.124(3) Angstroem, c = 10.412(2) Angstroem, alpha = 90.58(1) deg, beta = 112.29(2) deg, gamma = 97.53(2) deg.Complexes 1-3 all contain bidentate P,S-bonded ligands occupying two coordination positions of an approximately square planar metal centre.In each case, the coordination is completed by two double bonds of a cod ligand.In contrast, complex 4 contains a monodentate P-bonded ligand.

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Highly efficient and robust molecular ruthenium catalysts for water oxidation,
Catalysts | Special Issue : Ruthenium Catalysts – MDPI

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Intramolecular Electron-Transfer of Covalently-Linked Polypyridine Ruthenium(II)Rhodium(III) Binuclear Complexes in the Excited State. Observation of the Marcus Inverted Region

Ru(II)bpy2Mebpy-CH2CH(OH)CH2-MebpyRh(III)L2 (L=bpy.phen) (1) were newly synthesized.Intramolecular electron-transfer in excited 1 was studied with a time-correlated single photon counting method.In H2O, the excited Ru(II) complex exhibits a biexponential decay.The presence of a slow component suggests that the excited state can be repopulated by thermal activation from the (Ru(III)-Rh(II) and the direct process to the ground state lies in the Marcus Inverted region.

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Highly efficient and robust molecular ruthenium catalysts for water oxidation,
Catalysts | Special Issue : Ruthenium Catalysts – MDPI

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Design, synthesis, and biological evaluation of platensimycin analogues with varying degrees of molecular complexity

The molecular design, chemical synthesis, and biological evaluation of two distinct series of platensimycin analogues with varying degrees of complexity are described. The first series of compounds probes the biological importance of the benzoic acid subunit of the molecule, while the second series explores the tetracyclic cage domain. The biological data obtained reveal that, while the substituted benzoic acid domain of platensimycin is a highly conserved structural motif within the active compounds with strict functional group requirements, the cage domain of the molecule can tolerate considerable structural modifications without losing biological action. These findings refine our present understanding of theplatensimycin pharmacophore and establish certain structure-activity re lationships from which the next generation of designed analogues of thisnew antibiotic may emerge.

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Highly efficient and robust molecular ruthenium catalysts for water oxidation,
Catalysts | Special Issue : Ruthenium Catalysts – MDPI

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ATP3 and MTP3: Easily Prepared Stable Perruthenate Salts for Oxidation Applications in Synthesis

The Ley?Griffith tetra-n-propylammonium perruthenate (TPAP) catalyst has been widely deployed by the synthesis community, mainly for the oxidation of alcohols to aldehydes and ketones, but also for a variety of other synthetic transformations (e.g. diol cleavage, isomerizations, imine formation and heterocyclic synthesis). Such popularity has been forged on broad reaction scope, functional group tolerance, mild conditions, and commercial catalyst supply. However, the mild instability of TPAP creates preparation, storage, and reaction reproducibility issues, due to unpreventable slow decomposition. In search of attributes conducive to catalyst longevity an extensive range of novel perruthenate salts were prepared. Subsequent evaluation unearthed a set of readily synthesized, bench stable, phosphonium perruthenates (ATP3 and MTP3) that mirror the reactivity of TPAP, but avoid storage decomposition issues.

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Highly efficient and robust molecular ruthenium catalysts for water oxidation,
Catalysts | Special Issue : Ruthenium Catalysts – MDPI

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Catalytic ester-amide exchange using group (IV) metal alkoxide-activator complexes

A process for preparation of amides from unactivated esters and amines has been developed using a catalytic system comprised of group (IV) metal alkoxides in conjunction with additives including 1-hydroxy-7-azabenzotriazole (HOAt). In general, ester-amide exchange proceeds using a variety of structurally diverse esters and amines without azeotropic reflux to remove the alcohol byproduct. Initial mechanistic studies on the Zr(Ot-Bu)4-HOAt system revealed that the active catalyst is a novel, dimeric zirconium complex as determined by X-ray crystallography.

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Highly efficient and robust molecular ruthenium catalysts for water oxidation,
Catalysts | Special Issue : Ruthenium Catalysts – MDPI

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Intramolecular electronic energy transfer in ruthenium(II) diimine donor/pyrene acceptor complexes linked by a single C-C bond

The photophysical behavior of [(bpy)2Ru(L)]2+ complexes L = 4-(1′-pyrenyl)-2,2′-bipyridine, bpy-pyr; 2-(1′–pyrenyl)-1,10-phenanthroline, phen-pyr; and 2-(2′-naphthyl)-1,10-phenanthroline, phen-nap) was investigated in solutions and frozen matrices. The conformation of the linked pyrene differs in the two complexes: The pyrene moiety is conformationally constrained to be nearly perpendicular to the phenanthroline in the phen-pyr complex while the pyrene in the bpy-pyr complex has much greater flexibility about the C-C bond linking the ligand and the pyrene. The 3MLCT excited state of the Ru(II) diimine complex and the 3 (pi?pi*) state of the pyrenyl substituent are nearly isoenergetic; the 3MLCT state is the lowest energy state in the bpy-pyr complex, and the pyrene 3(pi?pi*) state is lower in energy for the phen-pyr complex. The bpy-pyr complex is unique in that the3MLCT state has a very long lived luminescence (approximately 50 mus in degassed CH3CN). Luminescence decays for both pyrene containing complexes can be fit as double exponentials, indicating that the 3MLCT and 3(pi?pi*) states are not in equilibrium. Analysis of decays obtained at several temperatures reveal that energy transfer is slower than relaxation of the 3MLCT state but more rapid than decay of the pyrene localized3(pi?pi*) state. The results also suggest that electronic coupling between the two states is weak despite the fact that the two chromophores are separated by a single covalent bond.

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Highly efficient and robust molecular ruthenium catalysts for water oxidation,
Catalysts | Special Issue : Ruthenium Catalysts – MDPI

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Preparation of ruthenium and osmium carbonyl complexes using microwave heating: demonstrating the use of a gas-loading accessory and real-time reaction monitoring by means of a digital camera

By using a gas-loading accessory, we show that it is possible to perform reactions involving gases and prepare organometallic complexes easily in good yields using microwave heating. The complexes Ru3(CO)12, H4Ru4(CO)12, and H2Os 3(CO)10 are prepared. Ligand substitution reactions of Ru3(CO)12 are also studied and, in the case of the reaction with triphenylphosphine, the reaction is monitored in real time by means of a digital camera interfaced with the microwave unit.

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Highly efficient and robust molecular ruthenium catalysts for water oxidation,
Catalysts | Special Issue : Ruthenium Catalysts – MDPI

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Furanyl cyclic amines: A diastereoselective synthesis of 2,6-syn-disubstituted piperidines under thermodynamic control

Utilising the propensity of the 2-furanyl group to facilitate equilibration of an adjacent tosylamide chiral centre, a diastereoselective route to 2,6-syn-piperidines was developed that proceeds with high levels of thermodynamic stereocontrol. X-ray crystallography structures suggest that, as seen in similar systems, pseudo-allylic strain between the N-tosyl group and the substituents at the 2 and 6 positions dominates stereochemical preference, overriding 1,3 diaxial interactions. The Royal Society of Chemistry 2012.

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Highly efficient and robust molecular ruthenium catalysts for water oxidation,
Catalysts | Special Issue : Ruthenium Catalysts – MDPI

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Nucleophilic substitution on a Ru-coordinated Cp ring by a carborane anion

The Cp ring in [RuCl(Cp)(PPh3)2] undergoes an apparent nucleophilic attack by the carbanion carb- (Hcarb = 2-Me-1,2-dlcarba-closo-dodecaborane), to give an H-/carb- exchange process, which is favoured by coordination of the hydride to the ruthenium centre.

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Highly efficient and robust molecular ruthenium catalysts for water oxidation,
Catalysts | Special Issue : Ruthenium Catalysts – MDPI