Synthesis, Characterization, Reactivity, and Linkage Isomerization of Ru(Cl) 2 (L)(DMSO) 2 Complexes (original) (raw)
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2. Ru(0)-azo imine-carbonyl and Ru(II)- pyridyl-azo-imidazole complexes
The reaction of 2-(3 0 -pyridylazo)imidazole (3 0 -PyaiH) or its 1-alkyl derivative, 3 0 -PyaiR, with Ru(CO) 3 (PPh 3 ) 2 has synthesized air stable, moisture insensitive, diamagnetic Ru complexes, [Ru(CO)(3 0 -PyaiR)(PPh 3 ) 2 ]. The ligands serve as an unsymmetric N,N 0 -chelating agent (N(imidazole) and N(azo) are abbreviated as N and N 0 , respectively). The X-ray structure determination of [Ru(CO)-(3 0 -PyaiH)(PPh 3 ) 2 ] shows a square pyramidal geometry. The square plane is made up of Ru, 2P, C(O), N(1), and with N(3) at the apex. Other spectroscopic studies (IR, UV-Vis, NMR) support the stereochemistry. Electrochemistry shows three consecutive anodic peaks (E pa ) and suggest irreversible redox responses of Ru(I)/Ru(0), Ru(II)/Ru(I), Ru(III)/Ru(II) and azo reductions. Oxidation by Cl 2 of [Ru(CO)(3 0 -PyaiR)(PPh 3 ) 2 ] has isolated the Ru(II)-complex as the perchlorate salt, [Ru(CO)(Cl)(3 0 -PyaiR)(PPh 3 ) 2 ](ClO 4 ). A solution of RuCl 3 and 3 0 -PyaiR in ethanol has isolated two isomers of the composition Ru(3 0 -PyaiR) 2 Cl 2 . They have been characterized by spectral and electrochemical data.
Polyhedron, 2013
Five trans-[Ru(P-P) 2 Cl 2 ] complexes were prepared by reacting RuCl 2 (PPh 3 ) 3 with P-P ligands {P-P = 3-hexyl-1,3-bis(diphenylphosphino)propane (hdppp) (1); = 1,3-bis(diphenylphosphino)propane (dppp) (2); = 1,2-bis(diphenylphosphino)ethane (dppe) (3); 1.1 0 -bis(diphenylphosphino)methane (dppm) (4); 1,2-bis(diphenylphosphino)ethylene (depe) (5)}. The complexes were characterized by an elemental analysis, IR, 1 H, 13 C and 31 P{1H}NMR, FAB-MS and TG/DTA. These Ru(II) complexes showed Ru(III)/Ru(II) quasireversible redox couple. The molecular structures of the complexes 1 and 3 were determined by X-ray crystallography, and their spectroscopic properties were studied. Another polymorph of 3 was reported in literature, the reported polymorph of 3 in this work crystallizes in P 1 space group, whereas, the previously reported polymorph crystallizes in C2/c space group. The two complexes adopt a distorted trans octahedral coordination and ruthenium(II) ions are located on a crystallographic centre of symmetry. Based on the optimized structures, computational investigations were carried out in order to determine the electronic structures of the complexes. The electronic spectra of 1 and 1 + in dichloromethane were calculated with the use of time-dependent DFT methods, and the electronic spectra of the transitions were correlated with the molecular orbitals of the complexes.
Ru (0)-azoimine-carbonyl and Ru (II)-pyridyl-azo-imidazole complexes
The reaction of 2-(3 0 -pyridylazo)imidazole (3 0 -PyaiH) or its 1-alkyl derivative, 3 0 -PyaiR, with Ru(CO) 3 (PPh 3 ) 2 has synthesized air stable, moisture insensitive, diamagnetic Ru complexes, [Ru(CO)(3 0 -PyaiR)(PPh 3 ) 2 ]. The ligands serve as an unsymmetric N,N 0 -chelating agent (N(imidazole) and N(azo) are abbreviated as N and N 0 , respectively). The X-ray structure determination of [Ru(CO)-(3 0 -PyaiH)(PPh 3 ) 2 ] shows a square pyramidal geometry. The square plane is made up of Ru, 2P, C(O), N(1), and with N(3) at the apex. Other spectroscopic studies (IR, UV-Vis, NMR) support the stereochemistry. Electrochemistry shows three consecutive anodic peaks (E pa ) and suggest irreversible redox responses of Ru(I)/Ru(0), Ru(II)/Ru(I), Ru(III)/Ru(II) and azo reductions. Oxidation by Cl 2 of [Ru(CO)(3 0 -PyaiR)(PPh 3 ) 2 ] has isolated the Ru(II)-complex as the perchlorate salt, [Ru(CO)(Cl)(3 0 -PyaiR)(PPh 3 ) 2 ](ClO 4 ). A solution of RuCl 3 and 3 0 -PyaiR in ethanol has isolated two isomers of the composition Ru(3 0 -PyaiR) 2 Cl 2 . They have been characterized by spectral and electrochemical data.
Inorg. Chem., 2014
A new tetradentate dinucleating ligand [1,1'-(4-methyl-1H-pyrazole-3,5-diyl)bis(1-(pyridin-2-yl)ethanol)] (Hpbl) containing an O/N mixed donor set of atoms has been synthesized and characterized by analytical and spectroscopic techniques. The Ru-Cl and Ru-aqua complexes containing this ligand of general formula [Ru II X(Hpbl)(trpy)] y+ (trpy = 2,2':6',2"-terpyridine; X = Cl, y = 1; X = H 2 O, y = 2) have been prepared and thoroughly characterized by spectroscopic and electrochemical techniques. The Ru-aqua complex 2 2+ , undergoes N->O linkage isomerization as observed electrochemically and the related thermodynamic and kinetic parameters are extracted from cyclic voltammetry experiments together with DIGISIM, a CV simulation package. Under basic conditions an additional isomer is observed where the pyrazolyl group in the Hpbl ligand is replaced by the geminal pyridyl group. Further structural and electronic characterization of all the isomers has been carried out by mean of DFT calculations.
A study on tailor made ruthenium sulfoxide complexes: Synthesis, characterization and application
Journal of the Serbian Chemical Society, 2014
In this study, a dinucleating spacer incorporating two 2-aminopyridine units was used to prepare seven novel dinuclear compounds. These molecules were characterized by elemental analyses, conductivity measurements, magnetic susceptibility, FT-IR, FAB-Mass, electronic, 1 H-NMR and 13 C{ 1 H}-NMR spectral studies. The complex [{trans,mer-RuCl 2 (DMSO) 3 } 2 (μ-5,5′-methylenebis(2-aminopyridine))]•2DMSO (2) was also characterized through 1 H-1 H COSY NMR. There are mainly three different formulations, [{cis,fac-RuCl 2 (SO) 3 } 2 (µ-MBAP)]•2SO; [{trans,mer-RuCl 2 (SO) 3 } 2 (µ-MBAP)]•2SO and [{trans-RuCl 4 (SO)} 2 (µ-MBAP)] 2-[X] 2 + ; where SO = DMSO / TMSO; MBAP = 5,5′-methylenebis(2-pyridinamine) and [X] + = [(DMSO) 2 H] + , Na + or [(TMSO)H] +. The coordination was found through cyclic nitrogen of the pyridine ring in an octahedral environment for both metal centres. The chemical behaviour of [{cis,fac-RuCl 2 (DMSO) 3 } 2 (μ-5,5′-methylenebis(2-pyridinamine))]•2DMSO (1) and (2) in aqueous solution with respect to time was observed by conductivity measurements and UV-Vis spectrophotometry. All complexes were found to possess prominent antibacterial activity against Escherichia coli in comparison to chloramphenicol and gatifloxacin.
Inorganic Chemistry, 2008
A reaction between the (4,0) isomer of Ru 2 (ap) 4 Cl and LiC≡CC 5 H 4 N leads to a (3,1) isomer of Ru 2 (ap) 4 (C≡CC 5 H 4 N) 2 1 (ap) anilinopyridinate anion), whereas a reaction involving the (3,1) isomer of Ru 2 (F 3 ap) 4 Cl and TBACl • H 2 O leads to (4,0) Ru 2 (F 3 ap) 4 Cl 2 (F 3 ap) 2-(2,4,6-trifluoroanilino)pyridinate anion). To our knowledge, these are the first documented examples for isomeric conversion involving diruthenium compounds with tetracarboxylate-type structures. The structural, electrochemical, and spectroscopic properties of 1 and 2 were examined. The reversible Ru 2 5+/6+ process of (3,1) [Ru 2 (F 3 ap) 4 Cl] + is located at 0.62 V in CH 2 Cl 2 , 0.1 M TBAP but shifts to 0.29 V upon formation of (3,1) Ru 2 (F 3 ap) 4 Cl 2 in CH 2 Cl 2 containing chloride from added TBACl • H 2 O and shifts even further to E 1/2) 0.10 V after generation of (4,0) Ru 2 (F 3 ap) 4 Cl 2 in solution. The 190 mV potential difference between the Ru 2 6+/5+ redox couples of (3,1) Ru 2 (F 3 ap) 4 Cl 2 and (4,0) Ru 2 (F 3 ap) 4 Cl 2 in chloride-containing media can be compared to a smaller potential difference of only 60 mV between the Ru 2 6+/5+ redox couples of (3,1) Ru 2 (F 3 ap) 4 Cl and (4,0) Ru 2 (F 3 ap) 4 Cl in CH 2 Cl 2 containing 0.1 M tetrabutylammonium perchlorate (TBAP) as supporting electrolyte. The larger ∆E 1/2 in the case of the bis-chloride complexes in solutions containing 0.1 M TBACl • H 2 O can be accounted for in large part by structural differences that manifest themselves in different strengths of axial coordination to the Ru 2 5+ form of the compounds.
Polyhedron, 2001
Reaction of 3-(2-methoxyphenyl)pyrazole with 1,2-bis(bromomethyl)benzene under phase-transfer conditions, followed by demethylation of the methoxyphenyl units with BBr 3 , affords the new ligand H 2 L in which two bidentate chelating units (pyrazolyl-phenol) are separated by a o-xylyl spacer. Reaction of H 2 L with [M(acac) 3 ] (M=Cr, Ru) afforded in each case two mononuclear products [M(L)(acac)] and [M(L)(HL)]. Crystal structure determinations of [M(L)(acac)] for both M =Cr and Ru show that the complexes have similar structures, with the ligand L 2 − folded such that it coordinates as a tetradentate chelate in a cis-N 2 ,cis-O 2 manner with the remaining two coordination sites at the metal occupied by the acac ligand. Neither complex [M(L)(HL)] formed X-ray quality crystals but we assume a similar mononuclear structure in which one L 2 − is coordinated as a tetradentate chelate, and the second (HL) − is coordinated via one bidentate N,O-binding site with the second site pendant and remaining protonated. [Ru(L)(acac)] undergoes reversible oxidation to Ru(IV) and an irreversible reduction to Ru(II); in contrast, for [Ru(L)(HL)] the Ru(III)-Ru(IV) and Ru(II)-Ru(III) couples are both reversible. A UV-Vis-NIR spectroelectrochemical study of [Ru(L)(HL)] was accordingly carried out, and shows that in the Ru(IV) state the spectrum develops intense, low-energy charge-transfer transitions in the near-IR region.
Inorganica Chimica Acta, 1996
The title compounds, mer-trichloro-cis-bis(I-methylimidazole)dimethyl sulfoxideruthenium(lII) (1) and 4-ethylpyridbtium rruns-(4ethylpyridine) (dimethyl sulfoxide)tetrachlororuthenate(III) (2) have been synthesized and structurally characterized. Crystals of 1 [RuCI,(C,H,N,),(C,H,oS)] .O.S(C,H,O) are monoclinic, space group P2/c with u= 16.836(g). b=8.646(3). C= 14.0.7(7) i\, /3=110.19(2)", Z=4. Crystals of 2 [RuCl,(C,H,N)(C,H,OS)][C,H,$I] are monoclinic, space group F2Jn with a=7.996(1), b= 11.670(I), c=23.979(3) A, p=98.39(1)". Z=4. The sulfoxide ligands are S-bonded and trwu to the N-planar ligands in botb Ru(lII) complexes.The two lMe-lm ligandsin 1 arecistoeachotherandthearrangementissuchthatitsB/B'interbasedihedralangleis65.6".B/RuL, and B'/RttL, dihedral angles are 26.8 and 66.8", respectively. The 4Et-Py plane in 2 bisects the Cl-Ru-CI bond angles. The conformatioo of the planar N-ligand observed in the X-ray structures is discussed in terms of an interaction between the ligsnds.