Ruthenium(II) complexes containing triphenylphosphine/triphenylarsine and bidentate Schiff bases derived from 2-hydroxy-1-naphthaldehyde and primary amines

The synthesis and characterisation of some new hexa-coordinated Schiff base complexes of the type [RuCl(CO)(EPh₃)(B)(L)] (E = P or As; B = PPh₃ or AsPh₃ or py or pip; L = anion of the Schiff bases derived from 2-hydroxy-1-naphthaldehyde and aniline, 4-chloroaniline or 2-methylaniline) are reported. I.r., electronic, ¹H-n.m.r, ³¹P-n.m.r. spectra, catalytic activity and antibacterial activity of the complexes are discussed. An octahedral structure has been tentatively proposed for all the complexes.     

Synthesis,characterization and catalytic studies of ruthenium(II) Schiff base complexes

Complexes of the type [Ru(CO)(EPh₃)(B)(L)] (E = P or As; B = PPh₃, AsPh₃, py or pip; L = dianion of the Schiff bases derived from the condensation of salicyloyl hydrazide with acetone, ethyl methyl ketone and salicylaldehyde have been synthesised by the reaction of equimolar amounts of [RuHCl(CO)(EPh₃)₂(B)] and Schiff bases in benzene. The resulting complexes have been characterized by analytical and spectral (i.r., electronic, n.m.r.) data. The arrangements of Ph₃P groups around the Ru metal was determined from ³¹P-n.m.r. spectra. An octahedral structure has been assigned to all the new complexes. All the complexes exhibit catalytic activity for the oxidation of benzyl alcohol and cyclohexanol in the presence of N-methylmorpholine-N-oxide as co-oxidant.     

Ruthenium(II) complexes containing bidentate Schiff bases and their antifungal activity

The reactions of ruthenium(II) complexes, [RuHCl(CO)(PPh₃)₂(B)] [B = PPh₃, pyridine (py) or piperidine (pip)], with bidentate Schiff base ligands derived by condensing salicylaldehyde with aniline, o-, m- or p-toluidine have been carried out. The products were characterised by analytical, i.r., electronic, ¹H-n.m.r. and ³¹P-n.m.r. spectral studies and are formulated as [RuCl(CO)(L)(PPh₃)(B)] (L = Schiff base anion; B = PPh₃, py or pip). An octahedral structure has been tentatively proposed for the new complexes. The Schiff bases and the new complexes were tested in vitro to evaluate their activity against the fungus Aspergillus flavus.     

Spectroscopic characterization and electrochemical studies of ruthenium(II) carbonyl complexes containing bidentate Schiff bases and triphenylphosphine or a nitrogen heterocycle

Reactions of ruthenium(II) carbonyl complexes of the type [RuHCl(CO)(PPh₃)₂(B)] [B?=?PPh₃, pyridine (py), piperidine (pip) or morpholine (mor)] with bidentate Schiff base ligands derived from the condensation of 2-hydroxy-1-naphthaldehyde with aniline, o-, m- or p-toluidine in a 1?:?1 mol ratio in benzene resulted in the formation of complexes formulated as [RuCl(CO)(L)(PPh₃)(B)] [L?=?bidentate Schiff base anion, B?=?PPh₃, py, pip, mor]. The complexes were characterized by analyses, IR, electronic and ¹H NMR spectroscopy, and cyclic voltammetric studies. In all cases, the Schiff bases replace one molecule of phosphine and a hydride ion from the starting complexes, indicating that Ru–N bonds in the complexes containing heterocyclic nitrogenous bases are stronger than the Ru–P bond to PPh₃. Octahedral geometry is proposed for the complexes.     

Ruthenium(II) carbonyl complexes with tridentate Schiff bases and their antibacterial activity

The products obtained by reacting ruthenium (II) complexes [RuHCl(CO)(PPh₃)₂(B)] [B = PPh₃, pyridine (py) or piperidine (pip)] with tridentate Schiff base ligands derived by condensing salicylaldehyde or o-vanillin with o-aminophenol and o-aminothiophenol, have been characterised by analytical, i.r., electronic, ¹H-n.m.r. and ³¹P-n.m.r. spectral studies and formulated as [Ru(L)(CO)(PPh₃)(B)] (L = bifunctional tridentate Schiff base anion, B = PPh₃, py or pip). An octahedral structure has been tentatively proposed for the new complexes. Some have been tested for the in vitro growth inhibitory activity against bacteria Escherichia coli, Bacillus sp. and Pseudomonas sp.     

Coordination complexes containing multidentate ligands : V. The reactions between trans-carbonylchlorobis(triphenylphosphine)iridium and trans-carbonylchloro(triphenylarsine)iridium and some tridentate group VB ligands

Bis[3-(dimethylarsino)propyl]phenylarsine, (tas), reacts with trans-Ir(CO)(EPh₃)₂ X (E = P, As; X = F, Cl, Br, I) to yield the (Ir(CO)(tas)] X complexes. In contrast, the similar ligand bis[3-(dimethylarsino)propyl]phenylphosphine, (dap), reacts with trans-Ir(CO)(EPh₃)₂X (E = P, As; X = Cl, Br, I) to yield a mixture of [Ir(CO)(dap)X] and [Ir(CO)(dap)]X, and with trans Ir(CO)(EPh₃)₂F (E = P, As) to yield solely [Ir(CO)(dap)F]. The cations [Ir(CO)(L)]⁺ (L = tas, dap) readily yield tetraphenylborate derivatives, [Ir(CO)(L)]BPh₄. The oxygenation of [Ir(CO)(tas)]⁺ in solution proceeds almost to completion after 15 h, whereas [Ir(CO)(dap)]⁺ does not appear to undergo oxygenation.     

Synthesis,spectral, electrochemical and catalytic studies of new Ru(III) tetradentate Schiff base complexes

The synthesis and characterization of several hexa‐coordinated ruthenium(III) Schiff base complexes of the type [RuX(EPh₃)(L)] (X = Cl or Br; E = P or As; L = dianion of the tetradentate Schiff base) are reported. IR, EPR, electronic spectra and cyclic voltammetric data of the complexes are discussed. An octahedral geometry has been tentatively proposed for all of these complexes. The new complexes have been subjected to catalytic activity in the reaction of oxidation of alcohols in the presence of N‐methylmorpholine‐N‐oxide. Copyright © 2007 John Wiley & Sons, Ltd.     

Ruthenium(II) unsymmetrical N2O2 tetradentate Schiff-base complexes: synthesis,characterization, and catalytic studies

A series of six-coordinate ruthenium(II) complexes [Ru(CO)(L ^x )(B)] (B = PPh₃, AsPh₃ or Py; L ^x = unsymmetrical tetradentate Schiff base, x = 5–8; L⁵= salen-2-hyna, L⁶= Cl-salen-2-hyna, L⁷= valen-2-hyna, L⁸= o-hyac-2-hyna) have been prepared by reacting [RuHCl(CO)(EPh₃)₂(B)] (E = P or As) with unsymmetrical Schiff bases in benzene under reflux. The new complexes have been characterized by analytical and spectroscopic (infrared, electronic, ¹H, ³¹P, and ¹³C NMR) data. An octahedral structure has been assigned for all the complexes. The new complexes are efficient catalysts for the transfer hydrogenation of ketones and also exhibit catalytic activity for the carbon–carbon coupling reactions.     

Catalytic and antimicrobial activities of new ruthenium(II) unsymmetrical Schiff base complexes

Hexa-coordinated ruthenium(II) complexes of the type [Ru(CO)(PPh₃)(Z)(L)] [Z = PPh₃, pyridine (py) or piperidine (pip); L = anion of the Schiff base] have been prepared by reacting [RuHCl(CO)(PPh₃)₂(Z)] with tridentate Schiff bases derived by condensing anthranilic acid with acetylacetone, salicylaldehyde, o-vanillin and o-hydroxyacetophenone. The complexes were characterised by analytical and spectral (i.r., electronic, ¹H- and ³¹P-n.m.r.) data, and were found to be effective catalysts for oxidising primary alcohols to aldehydes in the presence of N-methylmorpholine-N-oxide (NMO) as co-oxidant. The Schiff bases and their ruthenium(II) complexes show growth inhibitory activity against pathogenic fungi Aspergillus flavus, Fusarium oxysporium and Rhizoctonia solani.     

Synthesis,characterization and biocidal studies of ruthenium(II) carbonyl complexes containing tetradentate Schiff bases

Stable ruthenium(II) complexes of Schiff bases have been prepared by reacting [RuHCl(CO)(PPh₃)₂(B)] (B = PPh₃, pyridine or piperidine) with bis(o-vanillin)ethylenediimine (valen), bis(o-vanillin)propylene-diimine (valpn), bis(o-vanillin)tetramethylenediimine (valtn), bis(o-vanillin)o-phenylenediimine (valphn), bis(salicylaldehyde)tetramethylenediimine (saltn) and bis(salicylaldehyde)o-phenylenediimine (salphn). These complexes have been characterised by elemental analyses, i.r., electronic, ¹H- and ³¹P{¹H}-n.m.r. spectral studies. In all the above reactions, the Schiff bases replace two molecules of Ph₃P, a hydride and a halide ion from the starting complexes, indicating that the Ru–N bonds present in the complexes containing heterocyclic nitrogen bases are stronger than the Ru–P bond to Ph₃P. The new complexes of the general formula [Ru(CO)(B)(L)] (B = PPh₃, py or pip; L = tetradentate Schiff bases) have been assigned an octahedral structure. Some of the Schiff bases and the new complexes have been tested against the pathogenic fungus Fusarium sp.     

Luminescent property and catalytic activity of Ru(II) carbonyl complexes containing N, O donor of 2-hydroxy-1-naphthylideneimines

The reaction of the chelating ligands (obtained by the condensation of 2-hydroxy-1-naphthaldehyde with various primary amines) with [RuHCl(CO)(EPh3)2(B)] (where E=P; B=PPh3, py or pip: E=As; B=AsPh3) in benzene afforded new stable ruthenium(II) carbonyl complexes of the general formula [Ru(Cl)(CO)(EPh3)(B)(L)] (L=anion of bidentate Schiff bases). The structure of the new complexes was investigated using elemental analyses, spectral (FT-IR, UV-vis and 1H NMR) and electrochemical studies and is found to be octahedral. All the metal complexes exhibit characteristic MLCT absorption and luminescence bands in the visible region. The luminescence efficiency of the ruthenium(II) complexes was explained based on the ligand environment around the metal ion. These complexes catalyze oxidation of primary and secondary alcohols into their corresponding carbonyl compounds in the presence of N-methylmorpholine-N-oxide (NMO) as the source of oxygen. The formation of high valent Ru(IV)=O species as a catalytic intermediate is proposed for the catalytic process.     

Luminescent property and catalytic activity of Ru(II) carbonyl complexes containing N, O donor of 2-hydroxy-1-naphthylideneimines

The reaction of the chelating ligands (obtained by the condensation of 2-hydroxy-1-naphthaldehyde with various primary amines) with [RuHCl(CO)(EPh(3))(2)(B)] (where E=P; B=PPh(3), py or pip: E=As; B=AsPh(3)) in benzene afforded new stable ruthenium(II) carbonyl complexes of the general formula [Ru(Cl)(CO)(EPh(3))(B)(L)] (L=anion of bidentate Schiff bases). The structure of the new complexes was investigated using elemental analyses, spectral (FT-IR, UV-vis and (1)H NMR) and electrochemical studies and is found to be octahedral. All the metal complexes exhibit characteristic MLCT absorption and luminescence bands in the visible region. The luminescence efficiency of the ruthenium(II) complexes was explained based on the ligand environment around the metal ion. These complexes catalyze oxidation of primary and secondary alcohols into their corresponding carbonyl compounds in the presence of N-methylmorpholine-N-oxide (NMO) as the source of oxygen. The formation of high valent Ru(IV)=O species as a catalytic intermediate is proposed for the catalytic process.     

Tridentate Schiff base complexes of ruthenium(III) containing ONS/ONO donor atoms and their biocidal activities

New ruthenium(III) complexes of the [RuY(LL)(E)₂] type (Y = Cl or Br; LL = tridentate Schiff bases; E = PPh₃ or AsPh₃) have been synthesised by reacting [RuX₃(EPh₃)₃] (X = Cl, E = P; X = Cl or Br, E = As) or [RuBr₃(EPh₃)₂(MeOH)] with Schiff bases having the donor groups (O, N, X) viz., salicylaldehydethiosemicarbazone (X = S), salicylaldehydesemicarbazone (X = O), o-hydroxyacetophenonethiosemicarbazone (X = S) and o-hydroxyacetophenonesemicarbazone (X = O). The new complexes were characterised by elemental analysis, spectral (i.r., electronic spectra, e.p.r.), magnetic moment and cyclic voltammetry data. Biocidal activity studies were also carried out for the new complexes.     

Preparation, spectroscopy, EXAFS, electrochemistry and pharmacology of new ruthenium(II) carbonyl complexes containing ferrocenylthiosemicarbazone and triphenylphosphine/arsine

A new series of new hetero-bimetallic complexes containing iron and ruthenium of the general formula [RuCl(CO)(B)(EPh3)(L)] (where E=P or As; B=PPh3, AsPh3, py or pip; L=ferrocene derived monobasic bidentate thiosemicarbazone ligand) have been synthesized by the reaction between ferrocene-derived thiosemicarbazones and ruthenium(II) complexes of the type [RuHCl(CO)(B)(EPh3)2] (where E=P or As; B=PPh3, AsPh3, py or pip). The new complexes have been characterized by elemental analyses, IR, electronic, NMR (1H, 13C and 31P), EXAFS (extended X-ray absorption fine structure spectroscopy) and cyclic voltammetric techniques. Antibacterial activity of the new complexes has been screened against Escherichia coli, Vibrio cholerae, and Pseudomonas aeruginosa species.     

Studies on ruthenium(II) Schiff base complexes as catalysts for transfer hydrogenation reactions

The reactions of [RuHCl(CO)(B)(EPh₃)₂] (B = EPh₃ or Py; E = P or As) and Schiff bases in 1:1 molar ratio led to the formation of [RuCl(CO)(EPh₃)(B)(L)] (E = P or As; B = PPh₃, AsPh₃ or Py; L = Schiff base ligand). The new complexes have been characterized by analytical and spectroscopic (IR, electronic and ¹H NMR) data. They have been assigned an octahedral structure. The new complexes were found to catalyse the transfer hydrogenation of ketones.     

Synthesis,characterization and catalytic studies of ruthenium(II) chalconate complexes

Stable ruthenium(II) carbonyl complexes of the type [RuCl(CO)(EPh₃)(B)(L)] (E = P or As; B = PPh₃, AsPh₃ or Py; L = 2′‐hydroxychalcones) were synthesized from the reaction of [RuHCl(CO)(EPh₃)₂(B)] (E = P or As; B = PPh₃, AsPh₃ or Py) with 2′‐hydroxychalcones in benzene under reflux. The new complexes were characterized by analytical and spectroscopic (IR, electronic ¹H, ³¹P and ¹³C NMR) data. They were assigned an octahedral structure. The complexes exhibited catalytic activity for the oxidation of primary and secondary alcohols into their corresponding aldehydes and ketones in the presence of N‐methylmorpholine‐N‐oxide (NMO) as co‐oxidant and were also found to be efficient transfer hydrogenation catalysts. Copyright © 2008 John Wiley & Sons, Ltd.     

Synthesis,crystal structure and catalytic activity of ruthenium(II) carbonyl complexes containing ONO and ONS donor ligands

Diamagnetic ruthenium(II) complexes of the type [Ru(L)(CO)(B)(EPh₃)] [where E = As, B = AsPh₃; E = P, B = PPh₃, py (or) pip and L = dibasic tridentate ligands dehydroacetic acid semicarbazone (abbreviated as dhasc) or dehydroacetic acid phenyl thiosemicarbazone (abbreviated as dhaptsc)] were synthesized from the reaction of [RuHCl(CO)(B)(EPh₃)₂] (where E = As, B = AsPh₃; E = P, B = PPh₃, py (or) pip) with different tridentate chelating ligands derived from dehydroacetic acid with semicarbazide or phenylthiosemicarbazide. All the complexes have been characterized by elemental analysis, FT-IR, UV–Vis and ¹H NMR spectral methods. The coordination mode of the ligands and the geometry of the complexes were confirmed by single crystal X-ray crystallography of one of the complexes [Ru(dhaptsc)(CO)(PPh₃)₂] (5). All the complexes are redox active and are monitored by cyclic voltammetric technique. Further, the catalytic efficiency of one of the ruthenium complexes (5) was determined in the case of oxidation of primary and secondary alcohols into their corresponding aldehydes and ketones in the presence of N-methylmorpholine-N-oxide.     

含NS和NNSS供电子原子的钌(Ⅱ)羰基配合物

通过[RuHCl(CO)(PPh₃)₂(B)] (B=PPh₃, 吡啶 (py), 哌啶 (pip), 吗啉 (morph))与适当的席夫碱按1∶1的物质的量的比反应，合成了二齿和四齿席夫碱钌(Ⅱ)配合物。所用席夫碱配体通过S-苄基二硫代肼基甲酸酯与2,3-丁二酮(物质的量的比分别为1∶1和1∶2)的缩合反应制得。通过元素分析和多种物理化学方法对钌(Ⅱ)配合物和其席夫碱配体进行了表征。钌(Ⅱ)配合物为六配位的反磁性物质。用三种细菌对席夫碱配体及其钌(Ⅱ)配合物的抗微生物活性进行了筛选试验。     

Ruthenium(II) carbonyl complexes containing tetradentate Schiffbases

Ruthenium(II) carbonyl complexes of general formula [Ru(CO)(B)(L)] [where B = PPh3, pyridine (py), piperidine (pip); L = the dianionic tetradentate Schiff bases derived from the condensation of acetylacetone or benzoylacetone with ethylenediamine, propylenediamine or trimethylenediamine] have been synthesised by reacting [RuHCl(CO)(PPh3)2(B)] (B = PPh3, py or pip) with bis(acetylacetone)ethylenediimine, bis(acetylacetone)propylenediimine, bis(acetylacetone)trimethylenedi- imine, bis(benzoylacetone)ethylenediimine, bis(benzoylacetone)propylenediimine or bis(benzoylacetone)trimethylenediimine. The complexes were characterised onthe basis of elemental analyses, i.r., electronic and 1H- and 31P{1H}-n.m.r. spectral studies. This revised version was published online in June 2006 with corrections to the Cover Date.     

Ruthenium(II) complexes of hybrid 8‐hydroxyquinoline–thiosemicarbazone ligands: synthesis,characterization and catalytic applications

A series of new hexa‐coordinated ruthenium(II) hydroxyquinoline–thiosemicarbazone complexes of the type [Ru(CO)(EPh₃)(B)(L)] (E = P or As; B = PPh₃, AsPh₃ or Py; L = hydroxyquinoline–thiosemicarbazone) were synthesized by reacting ruthenium precursor complexes [RuHCl(CO)(EPh₃)₂(B)] (E = P or As; B = PPh₃, AsPh₃ or Py) with hydroxyquinoline–thiosemicarbazone ligands in ethanol. The new complexes were characterized by analytical and spectroscopic (FT‐IR, UV–visible, NMR (¹H, ¹³C and ³¹P) and fast atom bombardment (FAB)–mass spectrometric methods. Based on the spectral results, an octahedral geometry was assigned for all the complexes. The new complexes showed good catalytic activity for the conversion of aldehydes to amides in the presence of hydroxylamine hydrochloride–sodium bicarbonate and for the oxidation of alkanes into their corresponding alcohols and ketones in the presence of m‐chloroperbenzoic acid. The complexes also catalyzed the N‐alkylation of benzylamine in the presence of KOtBu in alcohol medium. Copyright © 2013 John Wiley & Sons, Ltd.