Cyclopalladated 2-phenyldihydrooxazole complexes with ethylenediamine, 2,2′-bipyridine,and bridging acetate ligands

The ¹H NMR, electronic absorption, and luminescence spectra, as well as voltammograms of the reduction and oxidation of the complexes [Pd(C∧N)(N∧N)]ClO₄ and [Pd(C∧N)(μ-OOCCH₃)]₂ [where (C∧N)⁻ is deprotonated 2-phenyl-4,5-dihydro-1,3-oxazole, and N∧N is ethylenediamine or 2,2′-bipyridine (bpy)] were compared. Magnetic nonequivalence of protons in the dihydrooxazole ring and upfield shift of the corresponding signals were observed as a result of anisotropic effect of the ring current in palladated phenyl substituents in the [Pd(C∧N)(μ-OOCCH₃)]₂ complex having a C ₂ symmetry. One-electron reduction wave of [Pd(C∧N)bpy]⁺ was assigned to ligand-centered electron transfer to the π* orbital of 2,2′-bipyridine, and two oxidation waves of [Pd(C∧N)(μ-OOCCH₃)]₂ were attributed to successive one-electron oxidations of the palladium centers. Low-temperature (77 K) phosphorescence of [Pd(C∧N)En]⁺ and [Pd(C∧N)bpy]⁺ was ascribed to optical transition localized on the metal-complex fragment {Pd(C∧N)} and to interligand charge transfer between the chelating and cyclopalladated ligands. The formation of metal-metal bond in the complex [Pd(C∧N)(μ-OOCCH3₎]₂ gives rise to radiative decay of photoexcitation energy from two electronically excited states, one of which is localized on the {Pd(C∧N)} fragment, and the second corresponds to the charge transfer metal-metal-cyclopalladated ligand.     

Synthesis,characterization, and cytotoxicity of Pt(IV) complexes containing 1,10-phenanthroline and 2,2′-bipyridine and diaminocyclohexane ligands

Four platinum(IV) complexes containing intercalating ligands [1,10-phenanthroline (phen) and 2,2′-bipyridine (bpy)] and ancillary ligands [(1S,2S)-diaminocyclohexane (SS-DACH) and (1R,2R)-diaminocyclohexane (RR-DACH)] were synthesized and characterized by ¹H nuclear magnetic resonance, electrospray ionization mass spectrometry, X-ray crystal structure analysis, elemental analysis, ultraviolet absorption spectroscopy, circular dichroism spectroscopy, and electrochemical analysis. The reactions between [Pt(phen)(SS-DACH)Cl₂]²⁺ and glutathione and Ac-CPFC-NH₂ were investigated by high-performance liquid chromatography. [Pt(phen)(SS-DACH)Cl₂]²⁺ was reduced to its corresponding Pt(II) complex [Pt(phen)(SS-DACH)]²⁺, while glutathione and Ac-CPFC-NH₂ were oxidized to glutathione-disulfide and a peptide containing an intramolecular disulfide bond, respectively. The cytotoxicities of the Pt(IV) complexes against a human non-small cell lung cancer cell line (A549) and the corresponding cisplatin-resistant cell line (A549cisR) were evaluated. These Pt(IV) complexes showed a higher activity toward A549 and A549cisR than did cisplatin. Also, the cytotoxicities of the Pt(IV) complexes were higher for A549cisR than for A549 cells. Moreover, the cytotoxicities of the (SS-DACH)-liganded platinum complexes were higher than those of the (RR-DACH)-liganded platinum complexes in either A549 or A549cisR cells. Phen-liganded platinum complexes were more cytotoxic than the bpy-liganded platinum complexes. The cytotoxicities of these Pt(IV) complexes had no correlation with reduction potentials.     

Bis(2,2′-bipyridine)cobalt(III) complexes containing asymmetric ligands: Synthesis,DNA-binding and photocleavage studies

Three new Co^III complexes: [Co(bpy)₂(pdtb)]³⁺ (1), [Co(bpy)₂(pdta)]³⁺ (2) and [Co(bpy)₂(pdtp)]³⁺ (3) have been synthesized and characterized. The DNA binding behavior of the Co^III complexes has been investigated by spectroscopic methods and viscosity measurements. The results indicate that the size and shape of the intercalated ligand have a marked effect on the binding affinity of complexes involving CT-DNA. Complexes (2) and (3) have been found to promote cleavage of plasmid pBR 322 DNA from the supercoiled form I to the open circular form II upon irradiation. Photocleavage mechanisms are proposed.     

Ruthenium(II) complexes containing 2,9-dimethyl-1,10-phenanthroline and 4,4′-dimethyl-2,2′-bipyridine as ancillary ligands: synthesis,characterization and DNA-binding

Two new Ruthenium (II) polypyridyl complexes [Ru(dmp)₂(ipbp)](ClO₄)₂ (1) (dmp = 2,9-dimethyl-1,10-phenanthroline, ipbp = 3-(1H-imidazo[4,5-f][1,10]phenanthrolin-2-yl)-4H-1-banzopyran-2-one) and [Ru(dmb)₂(ipbp)](ClO₄)₂ (2) (dmb = 4,4′-dimethyl-2,2′-bipyridine) have been synthesized and characterized by elemental analysis, FAB-MS, ES-MS and ¹H NMR and cyclic voltammetric methods. The DNA-binding behaviors of these complexes were investigated by spectroscopic titration, viscosity measurements, and thermal denaturation. Absorption titration and thermal denaturation studies reveal that these complexes are moderately strong binders of calf thymus DNA (CT-DNA). Viscosity measurements show that the complexes 1 and 2 interact with CT-DNA by intercalative mode. The DNA-binding affinity of the complex 2 is larger than that of complex 1.     

Synthesis of ruthenium and palladium complexes from glycosylated 2,2′-bipyridine and terpyridine ligands

A series of glucosylated mono- and di-(1H-1,2,3-triazol-4-yl)pyridines were prepared from glucosyl azides and 2-ethynyl and 2,6-diethynyl pyridine via Click reaction. Glucosylation of the silver salt of 4-hydroxy-2,2′-bipyridine with acetobromoglucose afforded the corresponding glucosylated 2,2′-bipyridine. Treatment of five examples of the latter pyridine ligands with [cis-Ru(bipy)2Cl₂], [Ru(tpy)Cl₃] or [Pd(COD)Cl₂] gave the corresponding ruthenium(II) and palladium(II) complexes in 62%-quantitative yield.     

Three trinuclear Ru(II) complexes containing 4,5-diazafluorene and 2,2′-bipyridine: synthesis,absorption spectrum,luminescence, and redox behavior

Three heterotopic ligands L¹, L², and L³ have been prepared by the reaction of 4,4′-bis(bromomethyl)-2,2′-bipyridine with 4,5-diazafluoren-9-oxime, 9-(2-hydroxy)phenylimino-4,5-diazafluorene, and 9-(4-hydroxy)phenylimino-4,5-diazafluorene, respectively, in DMF. The three ligands consist of two 4,5-diazafluorene units and one 2,2′-bipyridine unit. Ru(II) complexes [{Ru(bpy)₂}₃(μ₃-L^1?3)](PF₆)₆ (bpy = 2,2′-bipyridine) were prepared by refluxing Ru(bpy)₂Cl₂·2H₂O and the ligands in 2-methoxyethanol. The three Ru(II) complexes display metal-to-ligand charge-transfer absorption at 445–450 nm and one Ru(II)-centered oxidation at 1.32 V in CH₃CN solution at room temperature. Upon excitation into the metal-to-ligand charge-transfer band, the emission intensities of [{Ru(bpy)₂}₃(μ₃-L²)]⁶⁺ and [{Ru(bpy)₂}₃(μ₃-L³)]⁶⁺ are almost equal to that of [{Ru(bpy)₂}₃(μ₃-L¹)]⁶⁺ in CH₃CN solution at room temperature, but weaker than that of [{Ru(bpy)₂}₃(μ₃-L¹)]⁶⁺ in EtOH–MeOH (4?:?1, v/v) glassy matrix at 77 K.     

Dioxochromium(V) complexes with 1,10-phenanthroline and 2,2′-bipyridine ligands

cis-[Cr^III(phen)₂(H₂O)₂]³⁺ and cis-[Cr^III(bipy)₂(H₂O)₂]³⁺ (phen = 1,10-phenanthroline and bipy = 2,2-bipyridine) were readily oxidized by either PbO₂ or PhIO to form the chromium(V) complexes [Cr^V(phen)₂(O)₂]⁺ and [Cr^V(bipy)₂(O)₂]⁺ respectively, which were characterized by elemental analysis, i.r. and e.s.r. spectroscopy.     

Syntheses,structures and catalytic activities of low-coordinated rare-earth metal complexes containing 2,2′-pyridylpyrrolides

Reactions of the ligand precursors 2-(2′-pyridyl)-3,5-Me₂-pyrrole ( L ¹ H) and 2-(2-pyridyl)-3,4,5-Me₃-pyrrole ( L ² H) with [(Me₃Si)₂N]₃RE(μ-Cl)Li(THF)₃ in toluene afforded a series of low-coordinated rare-earth metal bis-amido complexes L ¹ RE[N(SiMe₃)₂]₂ [RE = Y ( 1a ), Dy ( 1b ), Er ( 1c ), Yb ( 1d )] and L ² RE[N(SiMe₃)₂]₂ [RE = Y ( 2a ), Dy ( 2b ), Er ( 2c ), Yb ( 2d )]. With the ionic radius of rare-earth metal increasing, the reaction of L ¹ H and [(Me₃Si)₂N]₃RE(μ-Cl)Li(THF)₃ gave dinuclear complexes ( L ¹ )₂RE(μ-Cl)(μ-η⁵:η¹:η¹- L ¹ )RE( L ¹ )[N(SiMe₃)₂]₂ [RE = Sm ( 1e ), Pr ( 1f )]; however, the reaction of L ² H and [(Me₃Si)₂N]₃Sm(μ-Cl)Li(THF)₃ afforded ( L ² )₂Sm[N(SiMe₃)₂]₂ ( 2e ). Results indicated that the ionic radius of rare-earth metal and subtle change in the ligands have substantial effects on the structure and bonding mode of complexes. The complexes showed a high catalytic activity for the ring-opening reaction of cyclohexene oxide with amines to afford various β-aminoalcohols under mild solvent-free conditions.     

Complexes of palladium,platinum and rhodium with 2,2′-biquinoline and 2-(2′-pyridyl)quinoline

Summary The reactions of 2,2-biquinoline(biq) with M(PhCN)₂X₂ (M=Pd; X=Cl or Br; M=Pt, X=Cl, Br or I), K₂PtCl₄ and RhCl₃·3H₂O and of 2-(2-pyridyl)quinoline (pq) with K₂PtCl₄ and RhCl₃·3H₂O have been investigated. The isolated complexescis-[Pd(biq)X₂] (X=Cl or Br),cis-[Pt(biq)Cl₂],cis-[Pt(biq)Cl₂]·H₂O,trans-[Pt(biq)₂Br₂]·5H₂O, [Pt₃(biq)₂I₆],mer-[Rh(biq)Cl₃-(H₂O)] andmer-[Rh(pq)Cl₃(H₂O)] have been characterized by elemental analyses, conductivity measurements, i.r., electronic, and¹H n.m.r. spectra. The reaction of pq with K₂PtCl₄ in 1M H₂SO₄ gave the salt 2-(2-pyridyl) quinolinium tetrachloroplatinate(II) pentahydrate, (pqH)₂[PtCl₄]·5H₂O; when the reaction was carried out in aqueous acetone,cis-[Pt(pq)Cl₂] was obtained. A new method for the synthesis ofcis-[Rh(biq)₂X₂]X (X=Cl or Br) is described; both compounds have been further characterized by¹H n.m.r.     

Ruthenium,osmium and rhodium-2,3-bis(2′-pyridyl)quinoxaline complexes

Ru₃(CO)₁₂ reacts with 2,3-bis (2-pyridyl)quinoxaline (dpq) in benzene in the presence of either 2,2(dipyridine (dpy) or pyridine (py) to give the mononuclear complexes Ru(CO)₃(dpq) (1) and Ru(CO)₂(dpq)(py) (2), respectively. On the other hand, reactions of Os₃(CO)₁₂ with dpq alone, or in the presence of dipyridine, yield only Os(CO)₃(dpq) (3). Spectroscopic studies of the three complexes were consistent with the proposed structures. Reactions of RuCl₃ with dpq, under reduced pressure in PhH/EtOH gave bis-[Ru(dpq)₂Cl₂]Cl (4). Magnetic measurements showed Ru^III, d⁵, to be in a low-spin electronic configuration. Three complexes, Rh₂(dpq)₂Cl₆ (5), [Rh(dpq)₂Cl₂]Cl (6) and Rh(dpq)(py)Cl₃ (7), were isolated from reactions of RhCl₃ with dpq. The type of product was dependent on the reactants and conditions. The complexes exhibit either irreversible or quasi-reversible ligand-based reductions. In addition, the zerovalent complexes (1)–(3) displayed one metal(based oxidation in their cyclic voltammograms, due to the formation of M⁺ species.     

Spectroscopic and electrochemical study of dinuclear and mononuclear copper complexes with the bidentate ligand of the 2,2′-diquinoline series

The newly synthesized complex (2) of copper(I) chloride with di-n-hexyl 2,2′-biquinoline-4,4′-dicarboxylate (L) was spectroscopically and electrochemically characterized. The X-ray diffraction study showed that the crystals of complex 2 consist of the dinuclear moieties [L₂Cu¹ ₂(μ-Cl)₂] containing Cu₂(μ-Cl)₂ clusters. Spectrophotometric studies and ESI-mass spec-trometric measurements showed that after the dissolution of complex 2 in acetonitrile (AN) and N-methyl-2-pyrrolidone (NMP), the solution contained not only the dinuclear complexes [L₂Cu¹ ₂(μ-Cl)₂] but also [L₂Cu¹]Cl, [LCu¹Cl(Sol)], and [Cu¹Cl(Sol)] (Sol is the solvent). The electrochemical data also confirm the conclusion that bridged dinuclear chloride complex 2 dissociates both in NMP and AN to form the tetrahedral bis-biquinoline complex [L₂Cu¹]Cl. In solutions of complex 2 in alcohols and _N,_N-dimethylformamide (DMF), only [L₂Cu¹]Cl and [Cu¹Cl(Sol)] are present. In EtOH, AN, and DMF, [Cu¹Cl(Sol)] undergoes disproportionation to [Cu¹¹Cl(Sol)] and Cu⁰.     

Homo- and heterodinuclear 2,2′-bipyrimidine-bridged complexes

[M(hfacac)₂(bpym)] complexes, where M = Co^II, Ni^II or Zn^II, hfacac = hexafluoroacetylacetonate and bpym = 2,2bipyrimidine; and [Cl₂M(bpym)M(hfacac)₂] complexes, where M = Co^II, Ni^II Mn^II or ZnII M = Ni^II; M = NiII or Zn^II and M = Zn^II; M = Ni^II and M = Co^II have been prepared and characterized by chemical analysis, conductance measurements, IR and electronic spectroscopies and magnetic susceptibility measurements (4.2–292K range). The dinuclear NiII–Ni^II, Co^II–Ni^II and Mn^II–Ni^II complexes are antiferromagnetic, with an intramolecular exchange parameter, J, of –2.3–8.9cm–1. Co^II and Mn^II are in a high spin state. The low temperature effect observed in monomers and in Ni^II–Zn^II dimers is considered a consequence of either an intermolecular antiferromagnetic interaction or the zero-field splitting in NiII.     

Ruthenium(III) mono (2,2′-bipyridine) complexes containing O,O-donor ligands and their oxidation properties for organic compounds

The new complexes [Ru^IIIbpyL₂](PF₆) and [Ru^IIIbpyLCl₂] [bpy = 2,2-bipyridine; HL = acetylacetone, trifluoroacetylacetone, benzoylacetone (Hbac), tropolone or maltol; HL = Hbac or dibenzoylmethane) have been prepared and characterized by spectroscopy. Their redox behaviour was studied by cyclic voltammetry. They effectively catalyze the oxidation of alcohols, alkanes and primary aromatic amines.     

pH-dependent syntheses and crystal structures, characterizations, and DFT calculations of complexes with 2,2′-biimidazole and terephthalic acid ligands

The divalent transition metal complexes [Zn(L)₂(H₂O)₂](Tere) (I), [Cd(L)₂(H₂O)₂](Tere]) (II) and [Cd(L)₂(HTere)₂] (III) (L = 2,2’-biimidazole, Tere = terephthalate) have been synthesized under hydrothermal conditions and characterized by elemental analysis, IR spectrum, thermal analysis and single-crystal X-ray diffraction analysis. Complexes II and III have the same starting materials but possess different frame-works and are prepared from H₂Biim and H₂Tere under hydrothermal conditions with different pH values. The crystal structures show I and II have the same coordination circumstances and are coordinated by two H₂O molecules and two neutral bidentate 2,2′-biimidazole ligands. The terephthalate acts as the counter anion. In contrast, complex III contains protonated carboxylate groups coordinated to the metal centre to give neutral species. Furthermore, based on the optimized structures, molecular frontier orbitals, Mulliken charges and IR spetra of complex I and III are investigated by density functional theory. Calculated results show that the energy gap (ΔE _L-H) between HOMO and LUMO of complex III is bigger than that of I. It is revealed that complex III is more stable, and this calculated estimation corresponds with experimental analysis of TGA curves.     

Bridging ligands comprising two or more di-2-pyridylmethyl or amine arms: Alternatives to 2,2′-bipyridyl-containing bridging ligands

Bridging ligands incorporating 2,2′-bipyridine as a chelating component have been utilised for several decades and are widely employed in coordination chemistry, supramolecular chemistry and materials synthesis. Such ligands form stable 5-membered chelate rings upon coordination to a metal. Two related chelating units, di-2-pyridylamine and di-2-pyridylmethane, which form 6-membered chelate rings when coordinated to a metal, have been studied far less as components of bridging ligands but have recently garnered significant levels of attention. Of around 140 reports on the incorporation of these moieties into bridging ligands some 75% have been published in the last 15 years. This review covers the synthesis of bridging ligands containing di-2-pyridylamine and di-2-pyridylmethane chelating moieties, and a survey of their coordination and supramolecular chemistry. Applications of the resulting systems as structural and functional models of enzyme active sites, and spin-crossover materials, and for investigations into anion–π interactions are covered.     

Cadmium(II) complexes containing 2,2′-dimethyl-4,4′-bithiazole ligand: synthesis,characterization, and crystal structure

Mononuclear and coordination polymer compounds of 2,2′-dimethyl-4,4′-bithiazole (dm4bt) ligand have been prepared by metallation of dm4bt with Cd(NO₃)₂ · 4H₂O and CdCl₂ · H₂O. The compounds were characterized by IR, ¹H NMR, UV–Vis spectroscopy, and X-ray crystallography. The structural study of [Cd(dm4bt)₂(NO₃)₂] · H₂O (1) shows that the complex is a monomeric seven-coordinate (CdN₄O₃) cadmium(II)-bithiazole system with two bidentate dm4bt and mono and bidentate nitrates. The structure of [Cd(dm4bt)Cl₂] _n (2) is a distorted octahedral environment around the cadmium(II) (CdN₂Cl₄) forming a 1-D coordination polymer as a result of bridging by two chlorides and 2-D structure from π–π stacking interactions.     

Synthesis,electrochemical properties and electro-oxidative polymerization of copper(II) and nickel(II) complexes with N′-benzoylthiourea ligands containing pyrrole groups

The synthesis of four N-benzoylthioureas containing pyrrole groups are described. The electrochemical behaviour of their copper(II) and nickel(II) complexes has been investigated in aprotic solvents by coulometry and by cyclic voltammetry which indicates that the electrochemical oxidation of copper complexes leads to the formation of Cu^II-benzylureate complexes. The oxidative polymerization of nickel complexes on platinum and a glassy carbon electrode, has been carried out in MeCN.The redox properties of the polymeric films formed have been examined by cyclic voltammetry. The films are catalytically active in the electroreduction of oxygen.     

Synthesis,resolution and application of 2,2′-bis(di-2-furylphosphino)-1,1′-binaphthalene

A six step synthesis and resolution of (±)-2,2′-bis(di-2-furylphosphino)-1,1′-binaphthalene 4 (TetFuBINAP) is described along with its use in asymmetric inter- and intramolecular Heck reactions.     

The chemistry of pyridine thiols and related ligands, Part 5. Synthesis and spectroscopy of nickel(II) and copper(II) complexes containing 1-oxopyridine-2-thione and 2,2′-bipyridine or 1,10-phenanthroline

Summary Reactions of bis(1-oxopyridine-2-thione) Ni^II or Cu^II with 2,2-bipyridine (bipy) or 1,10-phenanthroline (phen) yield complexes of stoichiometry: Ni(C₅H₄NOS)₂L {L = bipy, two isomers: (1) and (2), L = phen, one isomer (3)} and Cu(C₅H₄NOS)₂(phen)·0.75CHCl₃ (4). The spectroscopy (i.r., u.v.-vis., e.s.r.) and magnetism studies of the above complexes are described. On the basis of conductivity, the Cu^II-phen complex has been formulated as [Cu(C₅H₄NOS)(phen)₂][Cu(C₅H₄NOS)₃]·1.5CHCl₃ (4). The vis. absorption spectra support similar octahedral structures for the minor bipy isomer (2) and for the Ni^II-phen complex [(3)], whereas the major isomer [(1)] has a different structure. The e.s.r. spectrum of the Cu^II-phen complex (4) is commensurate with an elongated octahedral structure. New methods for the preparation and spectroscopy of M(C₅H₄NOS)₂ (M = Mn, Ni, Cu or Zn) compounds have been investigated.