Synthesis,crystal structures,DNA/bovine serum albumin binding,DNA cleavage and cytotoxicity of five mononuclear zinc(II) complexes

Five new mononuclear zinc(II) complexes containing ligands with extended planar phenanthroline moieties (dipyrido‐[3,2‐a:2′,3′‐c]phenazine (dppz) or dipyrido[3,2‐d:2′,3′‐f] quinoxaline (dpq)), namely [Zn(dppz)(acac)₂]⋅CH₃OH ( 1 ), [Zn(dppz)(dbm)(OAc)] ( 2 ), [Zn(dpq)(dbm) (OAc)] 1.5H₂O ( 3 ), [Zn(dpq)(tfnb)(OAc)] ( 4 ) and [Zn(dpq)(tfnb)₂] ( 5 ), where acac = acetylacetonate, tfnb = benzoyltrifluoroacetone and dbm = dibenzoylmethane, were synthesized and structurally characterized. The binding ability of complexes 1 – 5 with calf thymus DNA was investigated by spectroscopic titration methods and viscosity measurements. Results indicate that all complexes bind to calf thymus DNA via intercalative mode, and the DNA binding affinities of dppz complexes 1 and 2 are apparently stronger than those of dpq complexes 3 – 5 . DNA photocleavage experiments reveal that these complexes are efficient DNA cleaving agents and they are more active in UV‐A (365 nm) than in visible light. In particular, the in vitro cytotoxicity of the complexes for human cancer cell line A549 demonstrates that the five compounds have anticancer activity with low IC₅₀ values. Meanwhile, interaction of the complexes with bovine serum albumin investigated using UV–visible and fluorescence methods indicates that all complexes can quench the intrinsic fluorescence of bovine serum albumin in a static quenching process.     

Reactivity studies of cyclopentadienyl ruthenium(II), osmium(II) and pentamethylcyclopentadienyl iridium(III) complexes towards 2-(2′-pyridyl)imidazole derivatives

The reaction of [CpRu(PPh₃)₂Cl] and [CpOs(PPh₃)₂Br] with chelating 2-(2′-pyridyl)imidazole (N ∩ N) ligands and NH₄PF₆ yields cationic complexes of the type [CpM(N ∩ N)(PPh₃)]⁺ (1: M = Ru, N ∩ N = 2-(2′-pyridyl)imidazole; 2: M = Ru, N ∩ N = 2-(2′-pyridyl)benzimidazole; 3: M = Ru, N ∩ N = 2-(2′-pyridyl)-4,5-dimethylimidazole; 4: M = Ru, N ∩ N = 2-(2′-pyridyl)-4,5-diphenylimidazole; 5: M = Os, N ∩ N = 2-(2′-pyridyl)imidazole; 6: M = Os, N ∩ N = 2-(2′-pyridyl)benzimidazole). They have been isolated and characterized as their hexafluorophosphate salts. Similarly, in the presence of NH₄PF₆, [Cp∗Ir(μ-Cl)Cl]₂ reacts in dry methanol with N ∩ N chelating ligands to afford in excellent yield [Cp∗Ir(N ∩ N)Cl]PF₆ (7: N ∩ N = 2-(2′-pyridyl)imidazole; 8: N ∩ N = 2-(2′-pyridyl)benzimidazole). All the compounds have been characterized by infrared and NMR spectroscopy and the molecular structure of [1]PF₆, [2]PF₆ and [7]PF₆ by single-crystal X-ray structure analysis.     

Stereospecific synthesis and redox properties of ruthenium(II) carbonyl complexes bearing a redox-active 1,8-naphthyridine unit

Two stereoisomers of cis-[Ru(bpy)(pynp)(CO)Cl]PF₆ (bpy = 2,2′-bipyridine, pynp = 2-(2-pyridyl)-1,8-naphthyridine) were selectively prepared. The pyridyl rings of the pynp ligand in [Ru(bpy)(pynp)(CO)Cl]⁺ are situated trans and cis, respectively, to the CO ligand. The corresponding CH₃CN complex ([Ru(bpy)(pynp)(CO)(CH₃CN)]²⁺) was also prepared by replacement reactions of the chlorido ligand in CH₃CN. Using these complexes, ligand-centered redox behavior was studied by electrochemical and spectroelectrochemical techniques. The molecular structures of pynp-containing complexes (two stereoisomers of [Ru(bpy)(pynp)(CO)Cl]PF₆ and [Ru(pynp)₂(CO)Cl]PF₆) were determined by X-ray structure analyses.     

Synthesis,Structures and Photophysical Properties of Cationic Cyclometalated Iridium(III) Complexes Bearing N-Phenylcarbazole Group

Four cationic cyclometalated Ir^III complexes [(MeOPCz)₂Ir(bpy)]PF₆ ( 3 ), [(MeOPCz)₂Ir(dtb-bpy)]PF₆ ( 4 ), [(TFPCz)₂Ir(bpy)]PF₆ ( 5 ), and [(TFPCz)₂Ir(dtb-bpy)]PF₆ ( 6 ) were successfully synthesized using two new cyclometalated ligands 9-phenyl-3-(4-methoxypyridin-2-yl)-9H-carbazole (MeOPCz) 1 and 9-phenyl-3-(4-trifluoromethylpyridin-2-yl)-9H-carbazole (TFPCz) 2 in combination with 2,2'-bipyridine (bpy) and 4,4'-di-tert-butyl-2,2'-bipyridine (dtb-bpy) as ancillary ligands. These complexes adopt the distorted octahedral configuration, and the complexes 5 and 6 crystallize in the centrosymmetric space group C2/c. Emission wavelength of these complexes can be tuned from 583 nm to 628 nm by the substituents (methoxy, trifluoromethyl and tert-butyl groups) in ligands. All of these complexes show relatively high emission efficiencies (0.28–0.41) and short lifetimes (0.242–0.461 μs).     

Half-sandwich η-benzene Ru(II) complexes of pyridylpyrazole and pyridylimidazole ligands: Synthesis, spectra, and structure

New series of half-sandwich ruthenium(II) complexes supported by a group of bidentate pyridylpyrazole and pyridylimidazole ligands [(η⁶-C₆H₆)Ru(L²)Cl][PF₆] (1), [(η⁶-C₆H₆)Ru(HL³)Cl][PF₆] (2), [(η⁶-C₆H₆)Ru(L⁴)Cl][PF₆] (3), and [(η⁶-C₆H₆)Ru(HL⁵)Cl][PF₆] (4) [L², 2-[3-(4-chlorophenyl)pyrazol-1-ylmethyl]pyridine; HL³, 3-(2-pyridyl)pyrazole; L⁴, 1-benzyl-[3-(2′-pyridyl)]pyrazole; HL⁵, 2-(1-imidazol-2-yl)pyridine] are reported. The molecular structures of 1-4 both in the solid state by X-ray crystallography and in solution using ¹H NMR spectroscopy have been elucidated. Further, the crystal packing in the complexes is stabilized by C-H?X (X = Cl and π), N-H?Cl, and π-π interactions.     

Synthesis and structural studies of arene ruthenium and Cp*Rh/Cp*Ir complexes containing pyridylpyrazole- and pyridylthiazole-based ligands

The reactions of [(arene)RuCl₂]₂ (arene = p-cymene or benzene) and [Cp*MCl₂]₂ (M = Rh or Ir) with N,N′-bidentate chelating ligands 2-[3-(2-pyridyl)pyrazolyl]pyrimidine (L1) and 4-phenyl-(2-pyridyl)thiazole (L2) leads to the formation of mononuclear complexes of general formula [(arene)/Cp*M(L)Cl]PF₆. Eight such complexes have been prepared and characterized by spectroscopic techniques. In addition, five of the complexes were also characterized by single-crystal X-ray diffraction. These complexes have typical piano-stool geometries around the metal center, with five-membered metellacycles in which L1 and L2 both act as N,N′-chelating ligands. Moreover, L1 prefers to coordinate through its pyrimidine and pyrazolyl nitrogen atoms, rather than the pyridine nitrogen.     

Synthesis and Characterization of New Mononuclear Ru (II) PolypyridylComplexes with Catalytic Activity

In this work, we report the synthesis and physicochemical characterization of new chloro and aqua mononuclear Ru (II) complexes of formula [Ru(LLL)(dpp)Cl]PF₆ and [Ru(LLL)(dpp)OH₂](PF₆)₂ (LLL=tpy =2,2’ : 6’,2’’-terpyridine; tptz=2,4,6-tris(2-pyridyl)-1,3,5-triazine and dpp=2,3-bis(2-pyridil)pyrazine). For the complex [Ru(tptz)(dpp)Cl]PF₆, the complete structure was determined by X-ray diffraction. Catalytic studies of aqua-complexes revealed that they are active for the water oxidation reaction at pH 1 using cerium ammonium nitrate (CAN) as a sacrificial oxidant. Also, we were able to establish the reaction mechanism and rate constants of each stage of the catalytic cycle, turnover frequencies (TOFs), and turnover numberes (TONs). The experimental TON values for the aqua complexes were very close to the theoretical value of 7.5, indicating a high degree of recovery. DFT and TD-DFT calculations of electronic states for all complexes were consistent with experimental results and allowed the complete assignment of their UV-Visible bands and redox states.     

Ni(II), Pd(II), Cu(II) And Zn(II) complexes with N-(2-Pyridyl)Carbonylaniline (L), Syntheses and X-Ray Crystal structures of [Cu(L)2(H2O)2](No3)2, [Cu(L)2(H2O)2](Clo4)2 and [Zn(L)2(H2O)2](Clo4)2

Reaction of the N-(2-pyridyl)carbonylaniline ligand (L) with Cu(NO₃)₂, Cu(ClO₄)₂, Zn(ClO₄)₂, Ni(NO₃)₂ and PdCl₂ gives complexes with stoichiometry [Cu(L)₂(H₂O)₂](NO₃)₂, [Cu(L)₂(H₂O)₂](ClO₄)₂, [Zn(L)₂(H₂O)₂] (ClO₄)_2, [Ni(L)₂(H₂O)Cl](NO₃) and PdLCl₂. The new complexes were characterized by elemental analyses and infrared spectra. The crystal structures of [Cu(L)₂(H₂O)₂](NO₃)₂, [Cu(L)₂(H₂O)₂](ClO₄)₂, and [Zn(L)₂(H₂O)₂](ClO₄)₂ were determined by X-ray crystallography. The cation complexes [M(L)₂(H₂O)₂] contain copper(II) and zinc(II) with distorted octahedral geometry with two N-(2-pyridyl)carbonylaniline (L) ligands occupying the equatorial sites. The hexa-coordinated metal atoms are bonded to two pyridinic nitrogens, two carbonyl oxygens and two water molecules occupying the axial sites. Both the coordinated water molecules and uncoordinated amide NH groups of the N-(2-pyridyl)carbonylaniline (L) ligands are involved in hydrogen bonding, resulting in infinite hydrogen-bonded chains running in one and two-dimensions.     

Chemical and electrochemical synthesis,structure, photoluminescent properties,and biological activity of 4-methyl-N-[2-[(Z)-2-(2-pyridyl)alkyliminomethyl]phenyl]benzenesulfamide zinc(II) complexes

A series of Zn(II) complexes of the tridentate azomethine ligands, condensation products of 2-(N-tosylamino)benzaldehyde and 2-aminoalkylpyridines, were synthesized by chemical and electrochemical methods. All compounds were characterized on the basis of C, H, N elemental analysis, Fourier-transform infrared, ¹H nuclear magnetic resonance, UV–Vis, and photoluminescence studies. The local atomic structures of complexes were determined from analysis of extended X-ray absorption fine structure and X-ray absorption near-edge structure of Zn K-edges. The molecular structure of chloro-{4-methyl-N-[2-[(Z)-2-pyridyl)ethyliminomethyl]phenyl]benzenesulfamide}zinc(II) was determined by X-ray single-crystal diffraction. The fluorescence spectra show that these complexes in dimethyl sulfoxide solutions at room temperature emit bright blue luminescence at 435–461 nm with fluorescence quantum yields in the range of 0.20–0.31. The assignment and the nature of the bands in experimental UV–Vis spectra of complexes were analyzed using time-dependent density functional theory calculations B3LYP/6-31G(d). The azomethines and complexes of zinc have been screened for their antibacterial, protistocidal, and fungistatic activities against Penicillium italicum, Colpoda steinii, Escherichia coli 078, and Staphylococcus aureus P-209, and the results are compared with the activity of furazolidone, chloroquine, and Fundazol.     

Cationic half-sandwich complexes (Rh, Ir, Ru) containing 2-substituted-1,8-naphthyridine chelating ligands: Syntheses, X-ray structure analyses and spectroscopic studies

Reactions of the dinuclear complexes [(η⁶-arene)Ru(μ-Cl)Cl]₂ (arene = C₆H₆, p-ⁱPrC₆H₄Me) and [(η⁵-C₅Me₅)M(μ-Cl)Cl]₂ (M = Rh, Ir) with 2-substituted-1,8-naphthyridine ligands, 2-(2-pyridyl)-1,8-naphthyridine (pyNp), 2-(2-thiazolyl)-1,8-naphthyridine (tzNp) and 2-(2-furyl)-1,8-naphthyridine (fuNp), lead to the formation of the mononuclear cationic complexes [(η⁶-C₆H₆)Ru(L)Cl]⁺ {L = pyNp (1); tzNp (2); fuNp (3)}, [(η⁶-p-ⁱPrC₆H₄Me)Ru(L)Cl]⁺ {L = pyNp (4); tzNp (5); fuNp (6)}, [(η⁵-C₅Me₅)Rh(L)Cl]⁺ {L = pyNp (7); tzNp (8); fuNp (9)} and [(η⁵-C₅Me₅)Ir(L)Cl]⁺ {L = pyNp (10); tzNp (11); fuNp (12)}. All these complexes are isolated as chloro or hexafluorophosphate salts and characterized by IR, NMR, mass spectrometry and UV/Vis spectroscopy. The molecular structures of [1]Cl, [2]PF₆, [4]PF₆, [5]PF₆ and [10]PF₆ have been established by single crystal X-ray structure analysis.     

Desymmetrizing Heteroleptic [Cu(P^P)(N^N)][PF6] Compounds: Effects on Structural and Photophysical Properties,and Solution Dynamic Behavior

The preparation, characterization and electrochemical and photophysical properties of a series of desymmetrized heteroleptic [Cu(P^P)(N^N)][PF₆] compounds are reported. The complexes incorporate the chelating P^P ligands bis(2-(diphenylphosphanyl)phenyl)ether (POP) and (9,9-dimethyl-9H-xanthene-4,5-diyl)bis(diphenylphosphane) (xantphos), and 6-substituted 2,2′-bipyridine (bpy) derivatives with functional groups attached by –(CH₂)_n– spacers: 6-(2,2′-bipyridin-6-yl)hexanoic acid (1), 6-(5-phenylpentyl)-2,2′-bipyridine (2) and 6-[2-(4-phenyl-1H-1,2,3,triazol-1-yl)ethyl]-2,2′-bipyridine (3). [Cu(POP)(1)][PF₆], [Cu(xantphos)(1)][PF₆], [Cu(POP)(2)][PF₆], [Cu(xantphos)(2)][PF₆], and [Cu(xantphos)(3)][PF₆] have been characterized in solution using multinuclear NMR spectroscopy, and the single crystal structure of [Cu(xantphos)(3)][PF₆]^.0.5Et₂O was determined. The conformation of the 6-[2-(4-phenyl-1H-1,2,3,triazol-1-yl)ethyl]-substituent in the [Cu(xantphos)(3)]⁺ cation is such that the α- and β-CH₂ units reside in the xanthene ‘bowl’ of the xantphos ligand. The 6-substituent desymmetrizes the structure of the [Cu(P^P)(N^N)]⁺ cation and this has consequences for the interpretation of the solution NMR spectra of the five complexes. The NOESY spectra and EXSY cross-peaks provide insight into the dynamic processes operating in the different compounds. For powdered samples, emission maxima are in the range 542–555 nm and photoluminescence quantum yields (PLQYs) lie in the range 13–28%, and a comparison of PLQYs and decay lifetimes with those of [Cu(xantphos)(6-Mebpy)][PF₆] indicate that the introduction of the 6-substituent is not detrimental in terms of the photophysical properties.     

Spectral, structural and DFT studies of platinum group metal 3,6-bis(2-pyridyl)-4-phenylpyridazine complexes and their ligand bonding modes

Reactions of 3,6-bis(2-pyridyl)-4-phenylpyridazine (L^ph) with [(η⁶-arene)Ru(μ-Cl)Cl]₂ (arene = C₆H₆, p-ⁱPrC₆H₄Me and C₆Me₆), [(η⁵-C₅Me₅)M(μ-Cl)Cl]₂, (M = Rh and Ir) and [(η⁵-Cp)Ru(PPh₃)₂Cl] (Cp = C₅H₅, C₅Me₅ and C₉H₇) afford mononuclear complexes of the type [(η⁶-arene)Ru(L^ph)Cl]PF₆, [(η⁵-C₅Me₅)M(L^ph)Cl]PF₆ and [(Cp)Ru(L^ph)(PPh₃)]PF₆ with different structural motifs depending on the π-acidity of the ligand, electronic properties of the central metal atom and nature of the co-ligands. Complexes [(η⁶-C₆H₆)Ru(L^ph)Cl]PF₆1, [(η⁶-p-ⁱPrC₆H₄Me)Ru(L^ph)Cl]PF₆2, [(η⁵-C₅Me₅)Ir(L^ph)Cl]PF₆5, [(η⁵-Cp)Ru(PPh₃)(L^ph)]PF₆, (Cp = C₅H₅, 6; C₅Me₅, 7; C₉H₇, 8) show the type-A binding mode (see text), while complexes [(η⁶-C₆Me₆)Ru(L^ph)Cl]PF₆3 and [(η⁵-C₅Me₅)Rh(L^ph)Cl]PF₆4 show the type-B binding mode (see text). These differences reflect the more electron-rich character of the [(η⁶-C₆Me₆)Ru(μ-Cl)Cl]₂ and [(η⁵-C₅Me₅)Rh(μ-Cl)Cl]₂ complexes compared to the other starting precursor complexes. Binding modes of the ligand L^ph are determined by ¹H NMR spectroscopy, single-crystal X-ray analysis as well as evidence obtained from the solid-state structures and corroborated by density functional theory calculations. From the systems studied here, it is concluded that the electron density on the central metal atom of these complexes plays an important role in deciding the ligand binding sites.     

Synthesis,crystal structures,DNA binding and cleavage properties and protein binding activities of three mononuclear cobalt(II) complexes

Three new mononuclear cobalt(II) complexes containing ligands with extended planar quinoxaline moieties, {dipyrido[3,2‐a:2′,3′‐c]phenazine (dppz) or dipyrido[3,2‐d:2′,3′‐f]quinoxaline (dpq)}, viz. [Co(dppz)(acac)₂] · CH₃OH ( 1 ), [Co(dpq)(tfnb)₂] ( 2 ) and [Co(dpq)(dbm)₂] ( 3 ), where acac = acetylacetonate, tfnb = benzoyltrifluoroacetone and dbm = dibenzoylmethane, have been synthesized and structurally characterized as octahedral complexes. The binding ability of the complexes with calf thymus (CT)‐DNA has been investigated by spectroscopic and viscosity measurements. Results indicate that all complexes bind to CT‐DNA via intercalative mode, and the DNA binding affinity of dppz complex 1 is apparently stronger than that of dpq complexes 2 and 3 . Furthermore, DNA photocleavage experiments indicate that these complexes are efficient DNA cleaving agents in UV‐A (365 nm) and hydroxyl radical (HO^·), singlet oxygen (¹O₂) and superoxide anion (¹O₂^?) serve as the major cleavage active species. In addition, interaction of the complexes with bovine serum albumin (BSA) was investigated using UV ? visible and fluorescence methods, which indicated that all complexes could quench the intrinsic fluorescence of BSA in a static quenching process. Copyright © 2014 John Wiley & Sons, Ltd.     

Synthesis and structure of di(2-phenyl-8-quinolyl) diselenide and zinc bis[(2-phenyl-8-quinolyl)selenolate]

Di(2-phenyl-8-quinolyl) diselenide [2-(C₆H₅)C₉H₅NSe]₂ and zinc bis[(2-phenyl-9-quinolyl)selenolate], Zn [2-(C₆H₅)C₉H₅NSe]₂, have been synthesized. The molecular and crystal structure of the compounds were determined by X-ray structural analysis. The structures of the 2-phenyl-8-quinolylselenol ligand in the molecules of di(2-phenyl-8-quinolyl) diselenide and in the intracomplex compound of zinc are compared. The effect of the phenyl group in position 2 of the quinoline nucleus on the formation of the molecules and their packing in the crystal structure is discussed.     

二{桥-2，4，6-三[二(2-吡啶基)胺]-1，3，5-三嗪-N，N′，N ″，N′′′}·四氯合二锌(Ⅱ)的合成与晶体结构(英)

A dinuclear Zn(Ⅱ) complex C₆₆H₄₈Cl₄N₂₄Zn₂·2CH₃OH·2H₂O (1) was synthesized and characterized by X-ray crystallography. In the complex, two 2,4,6-tris[bis(2-pyridyl)amino]-1,3,5-triazine ligands are bridged together by two zinc(Ⅱ) ions and stacked in a parallel manner. CCDC: 267649.     

Ruthenium complexes of hexakis(cyanophenyl)[3]radialenes and their di(cyanophenyl)methane precursors: synthesis,photophysical, and electrochemical properties

The coordination chemistry of cross-conjugated ligands and the effect of cross-conjugation on the nature of metal–metal and metal–ligand interactions have received limited attention. To explore the effects of cross-conjugation eight ruthenium complexes were synthesized, mononuclear complexes of two isomeric cross-conjugated [3]radialenes [RuCp(PPh₃)₂(L)]PF₆ and [{RuCp*(dppe)}(L)]PF₆ (L?=?hexakis(4-cyanophenyl)[3]radialene, 2; hexakis(3-cyanophenyl)[3]radialene, 3), and dinuclear complexes [{RuCp(PPh₃)₂}₂(L)](PF₆)₂ and [{RuCp*(dppe)}₂(L)](PF₆)₂ of the diarylmethane precursors (L?=?4,4′-dicyanodiphenylmethane, 4; 3,3′-dicyanodiphenylmethane, 5) to the [3]radialenes. Considerable synthetic challenges allowed only clean isolation of mononuclear complexes of the multidentate radialenes 2 and 3. As expected, coordinating a positively charged metal induces a red shift for the π–π* transition in complexes of ligand 2, but unexpectedly a blue shift for the same transition in complexes of 3 was observed. This points to conformational differences for the [3]radialene in the ruthenium complexes of the para- (2) versus meta- (3) substituted hexaaryl[3]radialenes. Cyclic voltammetry indicates that the methylene spacer in 4 and 5 does not enable any interaction between metal centers and the absorption behavior is essentially as observed for [Ru(NCPh)(PPh₃)₂Cp]PF₆ and [Ru(NCPh)(dppe)Cp*]PF₆ but generally with a slight red shift in absorbance maxima.     

Structural Chemistry of Chiral Complexes. NMR and X-ray studies on Rh1 compounds of (S)-1-[bis(p-methylphenyl)phosphino]-2-[(p-methoxybenzyl)amino]-3-methylbutane

The Rh¹(diolefin)complexes [Rh(nbd)( 2 )][PF₆] [Rh(1,5-cod)( 2 )][PF₆], and [Rh((Z)-α -acetamidocinnamic acid)( 2 )][PF₆] ( 2 = the chiral P,N-ligand (S)-1-[bis(p-methylphenyl)phospino]-2-[p-methoxybenzyl)amino]-3-methylbutane have been prepared and characterized. These complexes exit as a mixture of isomers arising from different five-membered-ring conformations and diastereoisomers due to both the prochiral nitrogen and olefin ligands. The three-dimensional solutions structures of these complexes have been studied with the specific aim of understanding how the chiral pocket is built. Aspects of the exchange dynamics and their possible relevance to homogeneous hydrogenation are discussed The solid-state structure for the nbd complex, [Rh(nbd)( 2 )][PF₆], as well as detailed one- and two-dimensional ³¹P-, ¹³C-, and ¹H-NMR results are presented.     

Study of the Bonding Modes of Di‐2‐pyridyl ketoxime Ligand towards Ruthenium,Rhodium and Iridium Half Sandwich Complexes

The bonding modes of the ligand di‐2‐pyridyl ketoxime towards half‐sandwich arene ruthenium, Cp*Rh and Cp*Ir complexes were investigated. Di‐2‐pyridyl ketoxime {pyC(py)NOH} react with metal precursor [Cp*IrCl₂]₂ to give cationic oxime complexes of the general formula [Cp*Ir{pyC(py)NOH}Cl]PF₆ ( 1a ) and [Cp*Ir{pyC(py)NOH}Cl]PF₆ ( 1b ), for which two coordination isomers were observed by NMR spectroscopy. The molecular structures of the complexes revealed that in the major isomer the oxime nitrogen and one of the pyridine nitrogen atoms are coordinated to the central iridium atom forming a five membered metallocycle, whereas in the minor isomer both the pyridine nitrogen atoms are coordinated to the iridium atom forming a six membered metallacyclic ring. Di‐2‐pyridyl ketoxime react with [(arene)MCl₂]₂ to form complexes bearing formula [(p‐cymene)Ru{pyC(py)NOH}Cl]PF₆ ( 2 ); [(benzene)Ru{pyC(py)NOH}Cl]PF₆ ( 3 ), and [Cp*Rh{pyC(py)NOH}Cl]PF₆ ( 4 ). In case of complex 3 the ligand coordinates to the metal by using oxime nitrogen and one of the pyridine nitrogen atoms, whereas in complex 4 both the pyridine nitrogen atoms are coordinated to the metal ion. The complexes were fully characterized by spectroscopic techniques.     

The synthesis and structural analysis of cis -β-{(1,6-di(2′-pyridyl)(2,5-dibenzyl-2,5-diazahexane O(1,2-diazahexane))(1,2-benzoquinone diimine))ruthenium(II)} and related complexes

Several isomers are possible when N₄-tetradentate ligands coordinate to form metal complexes. Here we report the synthesis and structural analysis of cis-β-{[1,6-di(2′-pyridyl)(2,5-dibenzyl-2,5-diazahexane)(1,2-benzoquinone diimine)]ruthenium(II)} formed exclusively from the β-precusor, β-{[1,6-di(2′-pyridyl)(2,5-dibenzyl-2,5-diazahexane) (dimethylsulfoxide)chloride] ruthenium(II)} hexaflourophosphate. Ruthenium(II) complexes synthesised from 1,6-di(2′-pyridyl)-2,5-dibenzyl-2,5-diazahexane, produce only two isomers which can be separated by recrystallisation into α- and β-[Ru(picenbz₂)(dmso)Cl]PF₆ (where picenbz₂ is 1,6-di(2′-pyridyl)-2,5-dibenzyl-2,5-diazahexane). The distinctively different proton NMR spectra of the isomers are an especially convenient feature with which to assess separation. Isomeric structure of the precursor, α or β, is conserved upon coordination of a bidentate ligand, such as benzene-1,2-diamine, 4,5-dimethyl-benzene-1,2-diamine, naphthalene-2,3-diamine, 2,2′-bipyridine, 1,10-phenanthroline or dipyrido[3,2-d:2′3′-f] quinoxaline, to produce complexes of the type α- or β-[Ru(picenbz₂)(bidentate)](PF₆)₂. The synthesis, separation and characterisation of the α- and β-precursors and the α- and β-[Ru(picenbz₂)(bidentate)](PF₆)₂ complexes are reported. Moreover, the crystal structures have been determined for β-[Ru(picenbz₂)(dmso)Cl]PF₆.0.5H₂O (C₃₀H₃₇N₄O_1.5F₆PSClRu); it is triclinic, space group P 1, a?=?9.987, b?=?12.883, c?=?14.287?Å, α?=?72.11, β?=?78.65, γ?=?88.39° and Z?=?2 and β-[Ru(picenbz₂)(bqdi)](PF₆)₂, (C₃₄H₃₈N₆F₁₂P₂Ru) which is triclinic, space group P 1, with a?=?10.129, b?=?10.338, c?=?19.587?Å, α?=?104.42, β?=?93.36, γ?=?92.00° and Z?=?2. The structures were determined at room temperature and refined by least-squares methods to R?=?0.044 for 5109 and R?=?0.075 for 3057 non-zero diffractometer data, respectively, for the dmso and bqdi species above.     

Chloride substitution of [CpRu(dppf)Cl] with sulfur-containing ligands

The reactions of CpRu(dppf)Cl (1) with the sulfur-containing ligands, thiophenol HSPh, 2-mercaptopyridine C₅H₄N(SH), thiourea SC(NH₂)₂, vinylene trithiocarbonate SCS(CH)₂S and ethylene trithiocarbonate SCS(CH₂)₂S, yielded chloro-substituted derivatives, viz. the mono-ruthenium(II) complexes CpRu(dppf)(SPh) (2), [CpRu(dppf)(SC₅H₄NH)]BPh₄ (3)BPh₄, [CpRu(dppf)(SC(NH₂)₂]PF₆ (4)PF₆, [CpRu(dppf)(SCS(CH)₂S)]Cl (5)Cl and [CpRu(dppf)(SCS(CH₂)₂S)]Cl (6)Cl, respectively. Treatment of 1 with AuCl(SMe₂) in the presence of NH₄PF₆ gave [(CpRu(dppf)(SMe₂)]PF₆ (7)PF₆. The reaction of 1 or 6 with SnCl₂ resulted in cleavage of chloro and dithiocarbonate ligands, respectively, to give CpRu(dppf)SnCl₃ (8). All complexes were spectroscopically characterized and the structures of 2 and cationic complexes 4-7 were determined by single-crystal diffraction analyses.