Synthesis, DNA-binding and photocleavage studies of ruthenium complexes [Ru(bpy)2(mitatp)] and [Ru(bpy)2(nitatp)]

Two new ruthenium complexes [Ru(bpy)₂(mitatp)](ClO₄)₂1 and [Ru(bpy)₂(nitatp)](ClO₄)₂2 (bpy = 2,2′-bipyridine, mitatp = 5-methoxy-isatino[1,2-b]-1,4,8,9-tetraazatriphenylene, nitatp = 5-nitro-isatino[1,2-b]-1,4,8,9-tetraazatriphenylene) have been synthesized and characterized by elemental analysis, ¹H NMR, mass spectrometry and cyclic voltammetry. Spectroscopic and viscosity measurements proved that the two Ru(II) complexes intercalate DNA with larger binding constants than that of [Ru(bpy)₂(dppz)]²⁺ (dppz = dipyrido[3,2-a:2′,3′-c]phenazine) and possess the excited lifetime of microsecond scale upon binding to DNA. Both complexes can efficiently photocleave pBR322 DNA in vitro under irradiation. Singlet oxygen (¹O₂) was proved to contribute to the DNA photocleavage process, the ¹O₂ quantum yields was determined to be 0.43 and 0.36 for 1 and 2, respectively. Moreover, a photoinduced electron transfer mechanism was also found to be involved in the DNA cleavage process.     

X-ray structure, redox and spectroscopic properties of ruthenium phosphine complexes [Ru(tpy)(bpy)(PPh3)] and [Ru(tpy)(bpy)(PCy3)]

The synthesis and crystal structures of two new phosphine ruthenium polypyridine complexes [Ru(tpy)(bpy)(PR₃)]²⁺ with R = Ph (1), Cy (2) are reported. Their geometrical parameters are intimately related to the electronic and steric properties of the phosphine ligand. Electrochemical and UV-Vis analyses showed the influence of the substituents of the coordinated phosphorus atom on the Ru^III/Ru^II potential and on the frontier orbitals energy gap. The results are discussed in terms of steric effects and net donor power of the phosphine ligands.     

Plasticity of the five-membered chelate ring in [PdCl2(1,2-(PR2)2-1,2-C2B10H10)] complexes (R = H or Pr)

Gradient-corrected density functional theory applied to 1,2-diphosphino-1,2-dicarba-closo-dodecaborane, 1,2-(PH₂)₂-1,2-C₂B₁₀H₁₀, and its respective PdCl₂ complex presents a clear picture of the effect of complexation on the P-C_c-C_c-P fragments (C_c = cage carbon C1 or C2) in the structures. The complexation results in clear closing in the P-C_c-C_c angles and shortening of C_c-C_c bond, but only minor changes take place in the P-C_c-C_c-P torsion angle. Furthermore, complexation brings along shortening of the P-C_c bonds with concomitant increase of covalency, as revealed by atoms-in-molecules calculations. Although there is also change in the C_c-C_c distance in the cage, no significant change is involved in the bonding. These findings are compared with the results obtained by single-crystal X-ray study for [PdCl₂(1,2-(PⁱPr₂)₂-1,2-C₂B₁₀H₁₀)] and additional calculations carried out for [PdCl₂(1,2-(PH₂)₂-C₂H₄)].     

A new series of iodocarbonyl ruthenium (II) complexes with unsymmetrical phosphine-phosphine sulfide ligands of the type Ph2P(CH2)nP(S)Ph2, n = 1-4: Isolation and structural investigation

Hexa-coordinated chelate complex cis-[Ru(CO)₂I₂(P∩S)] (1a) {P∩S = η²-(P,S)-coordinated} and penta-coordinated non-chelate complexes cis-[Ru(CO)₂I₂(P∼S)] (1b-d) {P∼S = η¹-(P)-coordinated} are produced by the reaction of polymeric [Ru(CO)₂I₂]_n with equimolar quantity of the ligands Ph₂P(CH₂)_nP(S)Ph₂ {n = 1(a), 2(b), 3(c), 4(d)} in dichloromethane at room temperature. The bidentate nature of the ligand a in the complex 1a leads to the formation of five-membered chelate ring which confers extra stability to the complex. On the other hand, 1:2 (Ru:L) molar ratio reaction affords the hexa-coordinated non-chelate complexes cis,cis,trans-[Ru(CO)₂I₂(P∼S)₂] (2a-d) irrespective of the ligands. All the complexes show two equally intense terminal ν(CO) bands in the range 2028-2103 cm⁻¹. The ν(PS) band of complex 1a occurs 23 cm⁻¹ lower region compared to the corresponding free ligand suggesting chelation via metal-sulfur bond formation. X-ray crystallography reveals that the Ru(II) atom occupies the center of a slightly distorted octahedral geometry. The complexes have also been characterized by elemental analysis, ¹H, ¹³C and ³¹P NMR spectroscopy.     

Synthesis and characterization of Pd(II) and Pt(II) complexes with triazolopyrimidine derivatives: The crystal structure of [Pd2L2Cl4] where L = 5,7-dimethyl-1,2,4-triazolo[1,5-a]pyrimidine

The Pd(II) and Pt(II) complexes with triazolopyrimidine C-nucleosides L¹ (5,7-dimethyl-3-(2′,3′,5′-tri-O-benzoyl-β-d-ribofuranosyl-s-triazolo)[4,3-a]pyrimidine), L² (5,7-dimethyl-3-β-d-ribofuranosyl-s-triazolo[4,3-a]pyrimidine) and L³ (5,7-dimethyl[1,5-a]-s-triazolopyrimidine), [Pd(en)(L¹)](NO₃)₂, [Pd(bpy)(L¹)](NO₃)₂, cis-Pd(L³)₂Cl₂, [Pd₂(L³)₂Cl₄] · H₂O, cis-Pd(L²)₂Cl₂ and [Pt₃(L¹)₂Cl₆] were synthesized and characterized by elemental analysis and NMR spectroscopy. The structure of the [Pd₂(L³)₂Cl₄] · H₂O complex was established by X-ray crystallography. The two L³ ligands are found in a head to tail orientation, with a Pd?Pd distance of 3.1254(17) Å. L¹ coordinates to Pd(II) through N8 and N1 forming polymeric structures. L² coordinates to Pd(II) through N8 in acidic solutions (0.1 M HCl) forming complexes of cis-geometry. The Pd(II) coordination to L² does not affect the sugar conformation probably due to the high stability of the C-C glycoside bond.     

A solution thermodynamic study of the Cu(II) and Zn(II) complexes of EBTA: X-ray crystal structure of the dimeric complex [Cu2(EBTA)(H2O)3]2

The copper(II) complex of the acyclic EBTA ligand (H₄EBTA = 1,2-bis(2-aminoethoxy)benzene-N,N,N′,N′-tetraacetic acid) has been prepared and characterized by X-ray analysis. The two copper ions of the dinuclear unit present the same distorted octahedral coordination polyhedra. The EBTA ligand is shared between two copper coordination centres, with the formation of centrosymmetric dimers, which are linked in a supramolecular tridimensional structure via additional interactions through the coordinated waters molecules with adjacent carboxylic oxygen atoms. The stability and protonation constants of EBTA with Cu(II) and Zn(II) ions indicate a higher stability of these complexes with respect to the corresponding complexes with the more flexible EGTA ligand (H₄EGTA = ethyleneglycol-bis(2-aminoethylether)-N,N,N′,N′-tetraacetic acid). On the other hand, the lower stability of [Gd(EBTA)]⁻ than [Gd(EGTA)]⁻ results in a decreased overall selectivity (lower K_sel) of EBTA towards Gd(III) and suggests that this complex may undergoes transmetallation reactions under physiological conditions.     

Novel [Ru(polypyridine)(CO)2Cl2] and [Ru(polypyridine)2(CO)Cl]-type complexes: Characterizing the effects of introducing azopyridyl ligands by electrochemical, spectroscopic and crystallographic measurements

The reaction of ruthenium carbonyl polymer ([Ru(CO)₂Cl₂]_n) with azopyridyl compounds (2,2′-azobispyridine; apy or 2-phenylazopyridine; pap) generated new complexes, [Ru(azo)(CO)₂Cl₂] (azo = apy, pap). [Ru(apy)(CO)₂Cl₂] underwent photodecarbonylation to give a chloro-bridged dimer complex, whereas the corresponding pap complex ([Ru(pap)(CO)₂Cl₂]) was not converted to a dimer. The reactions of the chloro-bridged dimer containing the bpy ligand (bpy = 2,2′-bipyridine) with either apy or pap resulted in the formation of mixed polypyridyl complexes, [Ru(azo)(bpy)(CO)Cl]⁺. The novel complexes containing azo ligands were characterized by various spectroscopic measurements including the determination of X-ray crystallographic structures. Both [Ru(azo)(CO)₂Cl₂] complexes have two CO groups in a cis position to each other and two chlorides in a trans position. The azo groups are situated cis to the CO ligand in [Ru(azo)(bpy)(CO)Cl]⁺. All complexes have azo N-N bond lengths of 1.26-1.29 Å. The complexes exhibited azo-based two-electron reduction processes in electrochemical measurements. The effects of introducing azopyridyl ligands to the ruthenium carbonyl complexes were examined by ligand-based redox potentials, stretching frequencies and force constants of CO groups and bond parameters around Ru-CO moieties.     

DNA-binding and photocleavage studies of [Ru(phen)2(NMIP)]

A novel ligand 2′-(2″-nitro-3″,4″-methylenedioxyphenyl)imidazo[4′,5′-f][1,10]-phenanthroline (NMIP) and its complex [Ru(phen)₂(NMIP)]²⁺ have been synthesized and characterized by mass spectroscopy, ¹H NMR and cyclic voltammetry. Binding of the complex with calf thymus DNA (CT DNA) has been investigated by spectroscopic methods, viscosity and electrophoresis measurements. The experimental results indicate that [Ru(phen)₂(NMIP)]²⁺ binds to DNA via partial intercalative mode and the individual enantiomers of it bind to DNA in different rates. [Ru(phen)₂(NMIP)]²⁺ has also been found to promote cleavage of plasmid pBR 322 DNA from the supercoiled Form I to the open circular Form II upon irradiation.     

Ru(phen)2(bis-thioether) complexes: Synthesis and photosubstitution reactions

Three new ruthenium(II) complexes which contain two 1,10-phenanthroline units and a third bis-thioether chelate have been prepared and characterized. For two complexes, the X-ray structure shows a perfect fit between the two phen ligands and the bis-thioethers, with almost perfect C₂ symmetry for the Ru(phen)₂ unit and the S-containing ligand. This geometrical complementarity is also reflected by π-π stacking between the phen nuclei and the S-borne phenyl rings. In relatively harsher preparation conditions a ruthenium complex composed of one phenanthroline and two bis-thioethers is formed as a result of a scrambling reaction. When a bis-thioether chelate incorporated in a macrocycle also including a 6,6′-disubstituted-2,2′-bipyridine unit is used, ¹H NMR study shows that an exo S-bonded ruthenium(II) complex is obtained. In presence of chloride anions a photosubstitution reaction of the bis-thioether chelate takes place selectively and efficiently.     

Synthesis and structural characterization of adducts of silver(I) perchlorate with PR3 (R = Ph, cy, o-tolyl) and oligodentate aromatic bases derivative of 2,2′-bipyridyl, L, AgClO4:PR3:L (1:1:1)

Ten novel adducts of the form AgClO₄:PR₃:L (1:1:1) (R = Ph, cy, o-tolyl; L = 2,2′-bipyridyl (‘bpy’), 2,2′-biquinoline (‘bq’), bis(2-pyridyl)amine (‘dpa’), bis(2-picolyl)amine (‘dpca’)) have been synthesized and characterized by analytical, spectroscopic (IR, far-IR, ¹H and ³¹P NMR) and single crystal X-ray diffraction studies. The solid state molecular structures show that the complexes predominantly take the form [(R₃P)AgL]⁺X⁻, with a trigonal PAgN₂ coordination environment, where the approach of the anion or the solvent may perturb the planarity of the silver environment. The ClO₄ anion shows uni- or semi-bidentate coordination, except in the complexes AgClO₄:PR₃:dpca (1:1:1) (R = Ph and o-tolyl), where the anion remains uncoordinated and the dpca donor is a three-coordinate pincer-like ligand.     

Substituents effect on the electronic structure, spectra and photochemistry of [Ru(NH3)5(Py-X)] complexes

The diagrams of MLCT and d-d excited states of the complexes [Ru(NH₃)₅(py-X)]²⁺ are calculated using semiempirical CINDO/S method. Comparison of the relative energies of MLCT and d-d excited states leads to the understanding of the background of the rules, found earlier by Ford et al., that govern photochemical activity of the Ru(II) complexes under consideration.     

Bis(O2S2 macrocycle) complexes of palladium(II)

Two isomeric dibenzo-O₂S₂ macrocycles L¹ and L² have been synthesised and their coordination chemistry towards palladium(II) has been investigated. Two-step approaches via reactions of 1:1-type complexes, [cis-Cl₂LPd] (1a: L = L¹, 1b: L = L²), with different O₂S₂ macrocycle systems (L¹ and L²) have led to the isolation of the following bis(O₂S₂ macrocycle) palladium(II) complexes in the solid state: [Pd(L¹)₂](ClO₄)₂ (2a) and a mixture of [Pd(L¹)₂](ClO₄)₂ (2a) + [Pd(L²)₂](ClO₄)₂ (2b).     

Coordination chemistry of acrylamide 3: Synthesis, crystal structure and IR spectroscopic properties of dichloro-tetrakis(O-acrylamide)copper(II), [Cu(O-OC(NH2)CHCH2)4Cl2]

The molecular structure of copper(II) chloride complex with acrylamide (AAmCH₂CHCONH₂), [Cu(AAm)₄Cl₂], was determined using X-ray diffraction analysis. The complex crystallizes in the cubic space group I-43d with a = 17. 8310(2) Å, β = 90°, and V = 5669.27(11) ų for Z = 12. The acrylamide molecules bind to the metal center via the carbonyl oxygen atom (Cu-O 1.996 Å). The coordination geometry of the metal center in the complex involves a tetragonally distorted octahedral structure with four O-donor atoms of acrylamide bonded in the equatorial positions and two chlorides in the apical positions. Comparison of crystal structure data of acrylamide and metal acrylamide complexes of those formed with divalent transition metal chlorides has been summarized.     

A series of thiolato-bridged di- and trinuclear complexes derived from [Tp∗Rh(SPh)2(MeCN)] (Tp∗ = hydrotris(3,5-dimethylpyrazol-1-yl)borate)

Treatment of the Rh(III) complex [Tp∗Rh(SPh)₂(MeCN)] (1) with a series of late transition metal complexes resulted in the formations of thiolate-bridged di- and trinuclear complexes, which include the Rh(III)-Rh(I) complexes, [Tp∗RhCl(μ-SPh)₂Rh(cod)] (2) and [Tp∗RhCl(μ-SPh)₂Rh(PPh₃)₂], the Rh(III)-Pd(II) complexes, [Tp∗RhCl(μ-SPh)₂Pd(η³-C₃H₅)] (4), [{Tp∗Rh(MeCN)}(μ-SPh)₂PdCl₂] (5), and [{Tp∗RhCl(μ-SPh)₂}₂Pd] (6), and the Rh(III)-Pt(II) complex [{Tp∗RhCl(μ-SPh)₂}₂Pt] (7). Early-late transition metal complexes containing the Rh(III)-Re(I) and Rh(III)-Mo(0) metal centers, [Tp∗RhCl(μ-SPh)₂Re(CO)₄] and [{Tp∗Rh(CO)}(μ-SPh)₂Mo(CO)₄] were also prepared from 1. The X-ray analysis has been carried out to confirm the structures for 2, 4, 5, 6, and 7.     

Synthesis, structure and magnetic properties of an oxo-bridged dinuclear iron(III) complex [(TPyA)FFeOFeF(TPyA)](BF4)2 · 0.5MeOH (TPyA = tris(2-pyridylmethyl)amine) containing the FFeOFeF linkage

The reaction of [Fe^II(H₂O)₆](BF₄)₂ with tris(2-pyridylmethyl)amine (TPyA) and triethylamine in methanol under aerobic conditions forms [(TPyA)FFe^IIIOFe^IIIF(TPyA)](BF₄)₂ · 0.5MeOH (1), in which each Fe(III) ion is coordinated to a TPyA and an F⁻ ion as well as an oxo ion (O²⁻) linking two Fe(III) ions. 1 has offset face-to-face π-π interactions between the dimers, and possesses a supramolecular network structure. The magnetic susceptibility of 1 can be fit with g = 2.0, J/k_B = − 153 K (106 cm⁻¹), and θ = − 0.3 K [H = − 2JS_a · S_b]. These indicate that very strong antiferromagnetic interactions occur via the oxo bridge within the Fe(III) dimer and weak antiferromagnetic interactions between the dimers.     

Synthesis and structural characterization of adducts of silver(I) carboxylate salts AgX (X = CF3COO, CH3COO) with ER3 (E = P, As; R = Ph, cy, o-tolyl) and oligodentate aromatic bases derivative of 2,2′-bipyridyl, L, AgX:PR3:L (1:1:1)

Twenty-one adducts of the form AgX:ER₃:L (1:1:1) (X = CF₃COO (‘tfa’), CH₃COO (‘ac’), E = P, As; R = Ph, cy, o-tolyl; L = 2,2′-bipyridyl (‘bpy’)-based ligand) have been synthesized and characterized by analytical, spectroscopic (IR, far-IR, ¹H, ¹⁹F and ³¹P NMR) and single crystal X-ray diffraction studies. The resulting complexes are predominantly of the form [(R₃E)AgL]⁺X⁻, with a trigonal EAgN₂ coordination environment, the planarity of which may be perturbed by the approach of anion or solvent. The carboxylate anions have been found to be uni-, or semi-bidentate, or also completely ionic, as in the complexes [Ag(PPh₃)(bpy)(H₂O)](tfa) and [Ag(PPh₃)(dpk · H₂O)](tfa) (‘dpk · H₂O’ = bis(2-pyridyl)ketone (hydrated)). The complexes Agac:PPh₃:dpa (1:1:1) and Agac:P(o-tol)₃:dpa:MeCN (1:1:1:1) are dinuclear, with bridging unidentate acetate and terminal unidentate dpa (‘dpa’ = bis(2-pyridyl)amine).     

Synthesis,characterization, redox behavior,DNA and protein binding and antibacterial activity studies of ruthenium(II) complexes of bidentate schiff bases

Two new ruthenium(II) complexes of Schiff base ligands (L) derived from cinnamaldehyde and ethylenediamine formulated as [Ru(L)(bpy)₂](ClO₄)₂, where L¹ = N,N’-bis(4-nitrocinnamald-ehyde)ethylenediamine and L² = N,N’-bis(2-nitrocinnamaldehyde)-ethylenediamine for complex 1 and 2, respectively, were isolated in pure form. The complexes were characterized by physicochemical and spectroscopic methods. The electrochemical behavior of the complexes showed the Ru(III)/Ru(II) couple at different potentials with quasi-reversible voltammograms. The interaction of the complexes with calf thymus DNA (CT-DNA) using absorption, emission spectral studies and electrochemical techniques have been used to determine the binding constant, K_b and the linear Stern–Volmer quenching constant, K_SV. The results indicate that the ruthenium(II) complexes interact with CT-DNA strongly in a groove binding mode. The interactions of bovine serum albumin (BSA) with the complexes were also investigated with the help of absorption and fluorescence spectroscopy tools. Absorption spectroscopy proved the formation of a ground state BSA-[Ru(L)(bpy)₂](ClO₄)₂ complex. The antibacterial study showed that the Ru(II) complexes (1 and 2) have better activity than the standard antibiotics but weak activity than the ligands.     

Versatile coordination behaviour of Ph2AsCH2AsPh2 with Ru(II)

Treatment of ‘RuCl₃ · 3H₂O’ with Ph₂AsCH₂AsPh₂ (dpam) in hot EtOH gives either trans-[RuCl₂(dpam-As,As′)(dpam-As)₂] (1), or cis-[RuCl₂(dpam-As,As′)₂] (2), depending on the mole ratio. On exposure to light, solutions of 2 isomerise to trans-[RuCl₂(dpam-As,As′)₂] (3). Treatment of [RuCl₂(PPh₃)₃] with two equivalents of dpam in CH₂Cl₂ gave a mixture of two products, from which trans-[RuCl₂(PPh₃) (dpam-As,As′)(dpam-As)] (4) was isolated by recrystallisation. The crystal structures of 1-4 are reported. Complexes 1-3 in CH₂Cl₂ undergo electrochemical oxidation to Ru(III), and the Ru(III) form of 2 undergoes isomerisation on the voltammetric timescale to the Ru(III) form of 3.     

Crystal structures of [M(NTf2)3(H2O)n] (M = Eu and Yb) and a template effect of linear molecules on the 3D hydrogen bonding network structure of [Eu(NTf2)3(H2O)3]

Lewis acid catalysts [Eu(NTf₂)₃] and [Yb(NTf₂)₃] can be easily crystallized from a p-xylene solution in the presence of carboxylic acids and a small amount of water to give a trihydrate and a pentahydrate, respectively. In the crystallization of [Eu(NTf₂)₃(H₂O)₃], linear molecules such as n-alkanes and n-alkanoic acids act as templates to form crystals belonging to the trigonal space group with a hexagonal cylindrical structure, which is constructed by 3D hydrogen bonding network. On the other hand, [Eu(NTf₂)₃(H₂O)₃] crystallized in the cubic space group P2₁3 in the presence of a bulkier carboxylic acid, cyclohexanecarboxylic acid. In both [Eu(NTf₂)₃(H₂O)₃] crystals, ligands act as bidentate ligands coordinating to the Eu atom through two oxygen atoms. [Yb(NTf₂)₃] crystallized as a pentahydrate in the monoclinic space group P2₁/n, in which ligands coordinated to the Yb atom with only one oxygen atom.     

Cyclometalated ruthenium(II) complexes of benzo[h]quinoline (bzqH)[Ru(bzq)(NCMe)4], [Ru(bzq)(LL)(NCMe)2], and [Ru(bzq)(LL)2] (LL = bpy, phen)

Cyclometalation of benzo[h]quinoline (bzqH) by [RuCl(μ-Cl)(η⁶-C₆H₆)]₂ in acetonitrile occurs in a similar way to that of 2-phenylpyridine (phpyH) to afford [Ru(bzq)(MeCN)₄]PF₆ (3) in 52% yield. The properties of 3 containing ‘non-flexible’ benzo[h]quinoline were compared with the corresponding [Ru(phpy)(MeCN)₄]PF₆ (1) complex with ‘flexible’ 2-phenylpyridine. The [Ru(phpy)(MeCN)₄]PF₆ complex is known to react in MeCN solvent with ‘non-flexible’ diimine 1,10-phenanthroline to form [Ru(phpy)(phen)(MeCN)₂]PF₆, being unreactive toward ‘flexible’ 2,2′-bipyridine under the same conditions. In contrast, complex 3 reacts both with phen and bpy in MeCN to form [Ru(bzq)(LL)(MeCN)₂]PF₆ {LL = bpy (4) and phen (5)}. Similar reaction of 3 in methanol results in the substitution of all four MeCN ligands to form [Ru(bzq)(LL)₂]PF₆ {LL = bpy (6) and phen (7)}. Photosolvolysis of 4 and 5 in MeOH occurs similarly to afford [Ru(bzq)(LL)(MeCN)(MeOH)]PF₆ as a major product. This contrasts with the behavior of [Ru(phpy)(LL)(MeCN)₂]PF₆, which lose one and two MeCN ligands for LL = bpy and phen, respectively. The results reported demonstrate a profound sensitivity of properties of octahedral compounds to the flexibility of cyclometalated ligand. Analogous to the 2-phenylpyridine counterparts, compounds 4-7 are involved in the electron exchange with reduced active site of glucose oxidase from Aspergillus niger. Structure of complexes 4 and 6 was confirmed by X-ray crystallography.