Halogen exchange and scrambling between C-X and M-X' bonds in copper, nickel, and cobalt complexes of 6,6'-bis(bromo/chloromethyl)-2,2'-bipyridine. structural, electrochemical, and photochemical studies

The synthesis, reactivities, spectroscopic, electrochemical, and structural studies of copper(I), copper(II), nickel(II), and cobalt(II) complexes of 6,6'-bis(bromomethyl)-2,2'-bipyridine (bpy-Br2) and 6,6'-bis(chloromethyl)-2,2'-bipyridine (bpy-Cl2) have been reported. The copper(I) complex [CuI(bpy-Br2)2](ClO4) (1) has been obtained in two crystallographic modifications, in which the coordination geometry of the metal center has the D2d symmetry. The reaction between CuCl2.2H2O and bpy-Br2 has been followed spectrophotometrically at 45 degrees C over a period of 7 h, and a mechanism for the intramolecular halogen exchange and scrambling in the initially formed compound [CuII(bpy-Br2)Cl2] (5) has been proposed. Depending upon the reaction conditions, several halogen-exchanged products, namely [CuII(bpy-Br1.86Cl0.14)(Cl1.89Br0.11)] (2), [CuII(bpy-Br1.81Cl0.19)(Cl1.70Br0.30)(H2O)] (3), and [CuII(bpy-Br0.63Cl1.37)(Cl0.54Br1.46)] (4), have been isolated in crystalline form. The reaction between bpy-Cl2 and CuCl2.2H2O provides [CuII(bpy-Cl2)Cl2] (7) and [CuII(bpy-Cl2)Cl2(H2O)] (8), whereas CoCl2.6H2O and NiCl2.6H20 on reaction with bpy-Br2 under boiling condition produce [CoII(bpy-Br0.5Cl1.5)(ClBr)] (11) and [NiII(bpy-Br0.46Cl1.54)(Cl0.73Br1.27)(H2O)] (12), respectively. The X-ray structures determined for the 4-coordinate compounds 2, 4, and 7 show flattened tetrahedral geometry for the metal center with the D2 symmetry. Both 5-coordinate compounds 3 and 12 have square pyramidal geometry, and whereas the nickel(II) complex 12 has near-perfect geometry (tau = 0.015), considerable distortion is observed for the copper(II) complex 3 (tau = 0.25). Complexes [CuII(bpy-Cl2)Br2] (6) and [CuII(bpy-Br2)Br2] under boiling condition undergo photoreduction to produce the dimeric copper(I) complexes [{CuI(bpy-Cl1.30Br0.70)(mu-Br)}2](9) and [{CuI(bpy-Br2)(mu-Br)}2] (10), respectively. The fact that the photoreduction of [CuII(bpy-Cl2)Br2] (6) and [CuII(bpy-Br2)Br2] do not take place in absence of light has been established by spectrophotometric measurements. The crystal structures of 9 and 10 have been determined. The electrochemical behavior of all the copper complexes 1-10 has been studied in acetonitrile and dichloromethane. The E1/2 values for the CuI/CuII redox couples show strong solvent dependence and for a given system the E1/2 value is more positive in dichloromethane relative to that in acetonitrile. For the compounds [CuII(bpy-Br2-xClx)(Cl2-yBry)] (x = 0-2, y = 0-2), the E1/2 values become more positive with the increase of y value.     

Dioxygen reactivity of copper and heme-copper complexes possessing an imidazole-phenol cross-link

Recent spectroscopic, kinetics, and structural studies on cytochrome c oxidases (CcOs) suggest that the histidine-tyrosine cross-link at the heme a3-CuB binuclear active site plays a key role in the reductive O2-cleavage process. In this report, we describe dioxygen reactivity of copper and heme/Cu assemblies in which the imidazole-phenol moieties are employed as a part of copper ligand LN4OH (2-{4-[2-(bis-pyridin-2-ylmethyl-amino)-ethyl]-imidazol-1-yl}-4,6-di -tert-butyl-phenol). Stopped-flow kinetic studies reveal that low-temperature oxygenation of [CuI(LN4OH)]+ (1) leads to rapid formation of a copper-superoxo species [CuII(LN4OH)(O2-)]+ (1a), which further reacts with 1 to form the 2:1 Cu:O2 adduct, peroxo complex [{CuII(LN4OH)}2(O2(2-))]2+ (1b). Complex 1b is also short-lived, and a dimer Cu(II)-phenolate complex [CuII(LN4O-)]2(2+) (1c) eventually forms as a final product in the later stage of the oxygenation reaction. Dioxygen reactivities of 1 and its anisole analogue [CuI(LN4OMe)]+ (2) in the presence of a heme complex (F8)FeII (3) (F8 = tetrakis(2,6,-difluorotetraphenyl)-porphyrinate) are also described. Spectroscopic investigations including UV-vis, 1H and 2H NMR, EPR, and resonance Raman spectroscopies along with spectrophotometric titration reveal that low-temperature oxygenation of 1/3 leads to formation of a heme-peroxo-copper species [(F8)FeIII-(O2(2-))-CuII(LN4OH)]+ (4), nu(O-O) = 813 cm(-1). Complex 4 is an S = 2 spin system with strong antiferromagnetic coupling between high-spin iron(III) and copper(II) through a bridging peroxide ligand. A very similar complex [(F8)FeIII-(O2(2-))-CuII(LN4OMe)]+ (5) (nu(O-O) = 815 cm(-1)) can be generated by utilizing the anisole compound 2, which indicates that the cross-linked phenol moiety in 4 does not interact with the bridging peroxo group between heme and copper. This investigation thus reveals that a stable heme-peroxo-copper species can be generated even in the presence of an imidazole-phenol group (i.e., possible electron/proton donor source) in close proximity. Future studies are needed to probe key factors that can trigger the reductive O-O cleavage in CcO model compounds.     

Copper(I) and copper(II) complexes possessing cross-linked imidazole-phenol ligands: structures and dioxygen reactivity

Catalytic reduction of O2 to H2O, and coupling to membrane proton translocation, occurs at the heterobinuclear heme a3-CuB active site of cytochrome c oxidase. One of the CuB ligated histidines is cross-linked to a neighboring tyrosine (C-N bond; tyrosine C6 and histidine epsilon-nitrogen), and the protic residue of this cross-linked His-Tyr moiety is proposed to participate as both an electron and a proton donor in the catalytic dioxygen reduction event. To provide insight into the chemistry of such a moiety, we have synthesized and characterized tetra- and tridentate pyridylalkylamine chelate ligands {LN4OR and LN3OR (R = H or Me)}, which include an imidazole-phenol (or anisole) cross-link and their copper(I/II) complexes. [CuI(LN4OH)]B(C6F5)4 (1) reacts with dioxygen at -80 degrees C in THF, forming an unstable trans-mu-1,2-peroxodicopper(II)complex, which subsequently converts to a dimeric copper(II)-phenolate complex [{Cu(LN4O-)}2](B(C6F5)4)2 (5a). The close analogue [CuI(LN4OMe)]B(C6F5)4 (3) binds dioxygen reversibly at -80 degrees C in tetrahydrofuran. Stopped-flow kinetics of the reaction [CuI(LN3OH)]ClO4 (2) with O2 in CH2Cl2 indicate a steady formation of the purple dimeric product [{Cu(LN3O-)}2](ClO4)2 (5b), which has been analyzed in the temperature range from -40 to +20 degrees C, DeltaH = -9.6 (6) kJ mol-1, DeltaS = -168 (2) J mol-1 K-1 (k(-40 degrees C) = 1.05(4) x 106 and k(+20 degrees C) = 4.6(2) x 105 M-2 s-1). The X-ray crystal structures of 1, [CuII(LN3OH)(MeOH)(OClO3-)](ClO4) (4), 5a, and 5b are reported.     

Tuning the selectivity/specificity of fluorescent metal ion sensors based on N2S2 pyridine-containing macrocyclic ligands by changing the fluorogenic subunit: spectrofluorimetric and metal ion binding studies

Two new fluorescent chemosensors for metal ions have been synthesized and characterized, and their photophysical properties have been explored; they are the macrocycles 5-(2-quinolinylmethyl)-2,8-dithia-5-aza-2,6-pyridinophane (L5) and 5-(5-chloro-8-hydroxyquinolinylmethyl)-2,8-dithia-5-aza-2,6-pyridinophane (L6). Both systems have a pyridyl-thioether-containing 12-membered macrocycle as a binding site. The coordination properties of these two ligands toward CuII, ZnII, CdII, HgII, and PbII have been studied in MeCN/H2O (1:1 v/v) and MeCN solutions and in the solid state. The stoichiometry of the species formed at 25 degrees C have been determined from absorption, fluorescence, and potentiometric titrations. The complexes [CuL5](ClO4)(2).1/2MeCN, [ZnL5(H2O)](ClO4)2, [HgL5(MeCN)](ClO4)2, [PbL5(ClO4)2], [Cu3(5-Cl-8-HDQH-1)(L6H-1)2](ClO4)(3).7.5H2O (HDQ=hydroxyquinoline), and [Cu(L6)2](BF4)(2).2MeNO2 have also been characterized by X-ray crystallography. A specific CHEF-type response of L5 and L6 to the presence of ZnII and CdII, respectively, has been observed at about pH 7.0 in MeCN/H2O (1:1 v/v) solutions.     

Fast O2 binding at dicopper complexes containing Schiff-base dinucleating ligands

A new family of dicopper(I) complexes [CuI2RL](X)2 (R=H, 1X, R=tBu, 2X and R=NO2, 3X, X=CF3SO3, ClO4, SbF6, or BArF, BArF=[B{3,5-(CF3)2C6H3}4]-), where RL is a Schiff-base ligand containing two tridentate binding sites linked by a xylyl spacer, has been prepared and characterized, and its reaction with O2 has been studied. The complexes were designed with the aim of reproducing structural aspects of the active site of type 3 dicopper proteins; they contain two three-coordinate copper sites and a rather flexible podand ligand backbone. The solid-state structures of 1ClO4, 2CF3SO3, 2ClO4, and 3BArF.CH3CN have been established by single-crystal X-ray diffraction analysis. 1ClO4 adopts a polymeric structure in the solid state while 2CF3SO3, 2ClO4, and 3BArF.CH3CN are monomeric. The complexes have been studied in solution by means of 1H and 19F NMR spectroscopy, which put forward the presence of dynamic processes. 1-3BArF and 1-3CF3SO3 in acetone react rapidly with O2 to generate metaestable [CuIII2(mu-O)2(RL)]2+ 1-3(O2) and [CuIII2(mu-O)2(CF3SO3)(RL)]+ 1-3(O2)(CF3SO3) species, respectively, that have been characterized by UV-vis spectroscopy and resonance Raman analysis. Instead, reaction of 1-3BArF with O2 in CH2Cl2 results in intermolecular O2 binding. DFT methods have been used to study the chemical identities and structural parameters of the O2 adducts, and the relative stability of the CuIII2(mu-O)2 form with respect to the CuII2(mu-eta2:eta2-O2) isomer. The reaction of 1X, X = CF3SO3 and BArF, with O2 in acetone has been studied by stopped-flow UV-vis exhibiting an unexpected very fast reaction rate (k=3.82(4)x10(3) M-1 s-1, DeltaH=4.9+/-0.5 kJ.mol-1, DeltaS=-148+/-5 J.K-1.mol-1), nearly 3 orders of magnitude faster than in the parent [CuI2(m-XYLMeAN)]2+. Thermal decomposition of 1-3(O2) does not result in aromatic hydroxylation. The mechanism and kinetics of O2 binding to 1X (X=CF3SO3 and BArF) are discussed and compared with those associated with selected examples of reported models of O2-processing copper proteins. A synergistic role of the copper ions in O2 binding and activation is clearly established from this analysis.     

New insights into the visible-light-induced DNA cleavage activity of dipyridoquinoxaline complexes of bivalent 3d-metal ions

Dipyridoquinoxaline (dpq) complexes of bivalent 3d-metal ions, viz., [FeII(dpq)3](PF6)2 (1), [CoII(dpq)3](ClO4)2 (2), [NiII(dpq)3](ClO4)2 (3), [CuII(dpq)2(H2O)](ClO4)2 (4), [ZnII(dpq)3](ClO4)2 (5), and [ZnII(dpq)2(DMF)2](ClO4)2 (5a) (DMF = N,N-dimethylformamide), are prepared and their photoinduced DNA cleavage activity studied. Structural characterization for the complexes 1 and 5a is done by single-crystal X-ray crystallography. All the complexes show efficient binding propensity to calf thymus DNA with a binding constant (K) value of approximately 10(5) M(-1). Complexes 1, 2, and 4 show metal-based cyclic voltammetric responses at 1.2, 0.4, and 0.09 V (vs SCE) in DMF 0.1 M [Bun4N](ClO4) assignable to the respective FeIII/FeII, CoIII/CoII, and CuII/CuI couples. The NiII and ZnII complexes do not show any metal-based redox process. The dpq-based reductions are observed in the potential range of -1.0 to -1.7 V vs SCE. DNA melting and viscosity data indicate the groove-binding nature of the complexes. Control experiments using distamycin-A suggest a minor groove-binding propensity of the complexes. The complexes exhibit photoinduced cleavage of supercoiled pUC19 DNA in UV light of 365 nm. The diamagnetic d6-FeII and d10-ZnII complexes are cleavage-inactive on irradiation with visible light. The paramagnetic d7-CoII and d9-CuII complexes exhibit efficient DNA cleavage activity on photoirradiation at their respective d-d band. The paramagnetic d8-NiII complex displays only minor DNA cleavage activity on irradiation at its d-d band. The DNA cleavage reactions at visible light under aerobic conditions involve the formation of hydroxyl radical. The CoII complex shows photocleavage of DNA under an argon atmosphere. Theoretical calculations on the complexes suggest a photoredox pathway in preference to a type-2 process forming singlet oxygen for the visible-light-induced DNA cleavage activity of the 3d-metal complexes. The theoretical data also predict that the photoredox pathway is favorable for the 3d7-CoII and 3d9-CuII complexes to exhibit DNA cleavage activity, while the analogous 3d6-FeII and 3d8-NiII complexes are energetically unfavorable for the exhibition of such activity under visible light. The CoII and CuII complexes are better suited for designing and developing new metal-based PDT agents than their cleavage-inactive FeII, NiII, and ZnII analogues.     

Mono-, bi-, and trinuclear CuII-Cl containing products based on the tris(2-pyridylmethyl)amine chelate derived from copper(I) complex dechlorination reactions of chloroform

The ligand TMPA (tris(2-pyridylmethyl)amine) and its copper complexes have played a prominent role in recent (bio)inorganic chemistry studies; the copper(I) complex [CuI(TMPA)(CH3CN)]+ possesses an extensive dioxygen reactivity, and it is also known to effect the reductive dechlorination of substrates such as dichloromethane and benzyl and allyl chlorides. In this report, we describe a set of new analogues of TMPA, ligand 6TMPAOH, binucleating Iso-DO, and trinucleating SYMM. Copper(I) complexes with these ligands and a previously described binucleating ligand DO react with chloroform, resulting in reductive dechlorination and production of [CuIIx(L)Clx]x+ (x = 1, 2, or 3). X-ray crystal structures of [CuII(6TMPAOH)Cl]PF6, [CuII2(Iso-DO)Cl2](PF6)2, [CuII2(DO)Cl2](PF6)2, and [Cu3(SYMM)Cl3](PF6)3 are presented, and the compounds are also characterized by UV-vis and EPR spectroscopies as well as cyclic voltammetry. The steric influence of a pyridyl 6-substituent (in the complexes with 6TMPAOH, Iso-DO, and SYMM) on the solid state and solution structures and redox potentials are compared and contrasted to those chlorocopper(II) complexes with a pyridyl 5'-substituent (in [CuII2(DO)Cl2](PF6)2 and in [CuII(TMPA)Cl]+). Some insights into the reductive dechlorination process have been obtained by using 2H NMR spectroscopy in following the reaction of [Cu2(Iso-DO)(CH3CN)2](PF6)2 with CDCl3, in the presence or absence of a radical trap, 2,4-di-tert-butylphenol.     

Characterization of the [Ag(dmb)(2)(+)](n) oligomers (dmb = 1,8-diisocyano-p-menthane) in solution

The crystallographically characterized polymers [[Ag(dmb)(2)]Y](n) (Y = BF(4)(-), NO(3)(-), ClO(4)(-)) extensively dissociate in solution, contrarily to the Cu analogue, and common molecular weight determination techniques such as light scattering, osmometric, and intrinsic viscosity measurements fail to provide data allowing full characterization. Using pulsed NMR experiments, notably (13)C NMR T(1) (spin lattice relaxation time) and NOE (nuclear Overhauser enhancement) measurements on various ionic [[Ag(dmb)(2)]Y](n) materials (Y = BF(4)(-), NO(3)(-), ClO(4)(-)) and their related mononuclear [Ag (CN-t-Bu)(4)]Y salts in acetonitrile-d(3) (as comparative standards), the dipole-dipole spin lattice relaxation times (T(1)(DD)) of a selected quaternary (13)C probe are measured. These data allow us to extract the correlation times (tau(c)), which in turn permit us to estimate the volume of the tumbling species in solution. The comparison of the data between the [Ag(dmb)(2)(+)](n) and Ag(CN-t-Bu)(4)(+) species indicates the oligomeric nature of the former species, where the average number of Ag(dmb)(2)(+) approximately 8 (M(n) approximately 4000-5000).     

Macrocyclic nickel(II) complexes coligated by hydrosulfide and hexasulfide ions: syntheses, structures, and magnetic properties of [NiII2L(mu-SH)]+ and [(LNiII2)2(mu-S6)]2+

The borohydride complex [Ni(II)2L(mu-BH4)]+ (3) where L(2-) represents a sterically demanding hexaaza-dithiophenolate ligand reacts rapidly with elemental sulfur in acetonitrile at ambient temperature to produce the cationic complexes [Ni(II)2L(mu-SH)]+ (4) and [(Ni(II)2L) 2(mu-S6)]2+ (6). Both complexes were isolated as ClO4(-) or BPh4(-) salts and characterized by IR and UV/vis spectroscopy and X-ray crystallography. Complex 4 (also accessible from [Ni(II)2L(ClO4)]+ (5) and Na2S.9H2O) features an unprecedented N3Ni(II)(mu-SR)2(mu-SH)Ni(II)N3 core structure, the hydrosulfide ligand being deeply buried in the binding-cavity of the bowl-shaped [Ni(II)2L]2+ complex. In 6, a helical S6(2-) chain, with a structure reminiscent to that of plastic sulfur, is almost completely encapsulated by two [Ni(II)2L]2+ subunits. In contrast to other triply sulfur-bridged N3Ni(II)(SR)3Ni(II)N3 structures whose ground states are typically of S = 0, 4 reveals an S = 2 ground-state which is attained by a ferromagnetic exchange interaction between the two Ni(II) (S = 1) ions ( J = 18 cm (-1), H = -2JS1S2). Intradimer ferromagnetic exchange interactions are also present in 6 ( J = 23 cm (-1)). A qualitative explanation for this difference is offered.     

N,N,N ',N '-Tetrakis(2-pyridylmethyl)ethylenediamine and its analogues as hypodentate ligands. Synthesis and characterization of the rhodium(III), ruthenium(II), and palladium(II) complexes

New complexes of Rh(III), Ru(II), and Pd(II) with N,N,N',N'-tetrakis(2-pyridylmethyl)ethylenediamine (tpen) and its analogues have been prepared. The reaction of RhCl(3).nH(2)O with tpen is slow and allows one to isolate the products of three consecutive substitution steps: Rh(2)Cl(6)(tpen) (1), cis-[RhCl(2)(eta(4)-tpen)](+) (2), and [RhCl(eta(5)-tpen)](2+) (3). In acetonitrile the reaction stops at the step of the formation of cis-[RhCl(2)(eta(4)-tpen)](+), whereas [RhCl(eta(5)-tpen)](2+) is the final product of the further reaction in ethanol. Fully chelated [Rh(tpen)](3+) could not be obtained. Bis(acetylacetonato)palladium(II), Pd(acac)(2), reacts with tpen and its analogues, N,N,N',N'-tetrakis(2-pyridylmethyl)-1,3-propanediamine (tptn) and N,N,N',N'-tetrakis(2-pyridylmethyl)-(R)-1,2-propylenediamine (R-tppn), to give [Pd(eta(4)-tpen)](2+) (4), [Pd(eta(4)-tppn)](2+) (5), and [Pd(eta(4)-tptn)](2+) (6), respectively. Two pyridyl arms remain uncoordinated in these cases. The formation of unstable Pd(III) complexes from these Pd(II) complexes in solution was suggested on the basis of electrochemical measurements. Ruthenium(III) trichloride, RuCl(3).nH(2)O, is reduced to give a Ru(II) complex with fully coordinated tpen, [Ru(tpen)](2+) (7). The same product was obtained in a more straightforward reaction of Ru(II)Cl(2)(dimethyl sulfoxide)(4) with tpen. Electrochemical studies showed a quasi-reversible [Ru(tpen)](2+/3+) couple for [7](ClO(4))(2) (E(1/2) = 1.05 V vs Ag/AgCl). Crystal structures of [2](PF(6)).2CH(3)CN, [3](PF(6))(2).CH(3)CN, [6](ClO(4))(2), and [7](ClO(4))(2).0.5H(2)O were determined. Crystal data: [2](PF(6)).2CH(3)CN, monoclinic, C2, a = 16.974(4) A, b = 8.064(3) A, c = 13.247(3) A, beta = 106.37(2) degrees, V = 1739.9(8) A(3), Z = 2; [3](PF(6))(2).CH(3)CN, triclinic, P1, a = 11.430(1) A, b = 19.234(3) A, c = 8.101(1) A, alpha = 99.43(1) degrees, beta = 93.89(1) degrees, gamma = 80.10(1) degrees, V = 1729.3(4) A(3), Z = 2; [6](ClO(4))(2), orthorhombic, Pnna, a = 8.147(1) A, b = 25.57(1) A, c = 14.770(4) A, V = 3076(3) A(3), Z = 4; [7](ClO(4))(2).0.5H(2)O, monoclinic, P2(1)/c, a = 10.046(7) A, b = 19.049(2) A, c = 15.696(3) A, beta = 101.46(3) degrees, V = 2943(2) A(3), Z = 4.     

Polymeric silver(I) complexes with pyridyl dithioether ligands: experimental and theoretical investigations on the coordination properties of the ligands

The reactions of four flexible tetradentate ligands, 1,3-bis(2-pyridylthio)propane (L1), 1,4-bis(2-pyridylthio)butane (L2), 1,5-bis(2-pyridylthio)pentane (L3) and 1,6-bis(2-pyridylthio)hexane (L4) with AgX (X = BF4-, ClO4-, PF6-, or CF3SO3-) lead to the formation of seven new complexes: [AgL1(BF4)]2 (1), [[AgL2](ClO4)]infinity (2), [[AgL2(CH3CN)](PF6)]infinity (3), [[AgL3](BF4)(CHCl3)]2 (4), [[AgL3(CF3SO3)](CH3OH)(0.5)]infinity (5), [[Ag2L4(2)](BF4)2]infinity (6), and [[AgL4](PF6)]infinity (7), which have been characterized by elemental analyses, IR spectroscopy, and X-ray crystallography. Single-crystal X-ray analyses show that complexes 1 and 4 possess dinuclear macrometallacyclic structures, and complexes 2, 3 and 5-7 take chain structures. In all the complexes, the nitrogen atoms of ligands preferentially coordinate to silver atoms to form normal coordination bonds, while the sulfur atoms only show weak interactions with silver atoms and the intermolecular AgS weak contacts connect the low-dimensional complexes into high-dimensional supramolecular networks. Additional weak interactions, such as pi-pi stacking, F...F weak interactions, Ag...O contacts or C-H...O hydrogen bonds, also help to stabilize the crystal structures. It was found that the parity of the -(CH2)n- spacers (n = 3-6) affect the orientation of the two terminal pyridyl rings, thereby significantly influence the framework formations of these complexes. The coordination features of ligands and their conformation changes between free and coordination states have been investigated by DFT calculations.     

Synthesis and structures of one- and two-electron oxidized forms of bis(acetylene)tetrairon clusters Cp'(4)Fe(4)(HCCH)(2) (Cp' = Cp,eta5-C(5)H(4)Me)

Air-oxidation of Cp'(4)Fe(4)(HCCH)(2) (Cp' = Cp (1a), C(5)H(4)Me (1b)) in an NH(4)PF(6)/CH(3)CN solution afforded the one-electron oxidized clusters [Cp'(4)Fe(4)(HCCH)(2)](PF(6)). Oxidation of 1a with excess AgBF(4) in THF afforded [1a](BF(4)), while that of 1b with excess AgBF(4) gave [1b](BF(4))(2). The X-ray crystal structure analysis of [1a](BF(4)) revealed that the monocationic cluster retains the butterfly-type Fe(4)(mu4-eta(2):eta(2):eta(1):eta(1)-HCCH)(2) framework similar to that of the neutral cluster. The average Fe-Fe bond length is shorter by 0.029 A than that in the neutral cluster. Electrochemical oxidation of 1a and 1b in 0.1 M NH(4)PF(6)/CH(3)CN solution at +0.30 and +0.25 V versus Ag/10 mM AgNO(3), respectively, afforded the two-electron oxidized clusters [1a](PF(6))(2) and [1b](PF(6))(2). The X-ray crystal structure analysis for [1b](BF(4))(2) shows that the butterfly-type cluster core is retained but shrinks more of those of neutral and monocationic clusters. The four Fe-Fe bonds in [1b](BF(4))(2) are unequivalent: one Fe-Fe bond (2.397(1) A) is apparently shorter than the others (2.439(2)-2.461(2) A).     

Mononuclear and binuclear copper(I) complexes ligated by bis(3,5-diisopropyl-1-pyrazolyl)methane: insight into the fundamental coordination chemistry of three-coordinate copper(I) complexes with a neutral coligand

By using the neutral bidentate nitrogen-containing ligand, bis(3,5-diisopropyl-1-pyrazolyl)methane (L1' '), the copper(I) complexes [Cu(L1' ')2](CuCl2) (1CuCl2), [Cu(L1' ')2](ClO4) (1ClO4), [Cu(L1' ')]2(ClO4)2 (2ClO4), [Cu(L1' ')]2(BF4)2 (2BF4), [Cu(L1' ')(NCMe)](PF6) (3PF6), [Cu(L1' ')(PPh3)](ClO4) (4ClO4), [Cu(L1' ')(PPh3)](PF6) (4PF6), [{Cu(L1' ')(CO)}2(mu-ClO4)](ClO4) (5ClO4), and the copper(II) complexes [{Cu(L1' ')}2(mu-OH)2(mu-ClO4)2] (6), and [Cu(L1' ')Cl2] (7) were systematically synthesized and fully characterized by X-ray crystallography and by IR and 1H NMR spectroscopy. In the case of copper(II), ESR spectroscopy was also applied. In comparison with the related neutral tridentate ligand L1', bis-chelated copper(I) complexes and binuclear linear-coordinated copper(I) complexes are easy to obtain with L1' ', like 1CuCl2, 1ClO4, 2ClO4, and 2BF4. Importantly, stronger and bulkier ligands such as acetonitrile (3PF6) and especially triphenylphosphine (4ClO4 and 4PF6) generate three-coordinate structures with a trigonal-planar geometry. Surprisingly, for the smaller ligand carbon monoxide, a mononuclear three-coordinate structure is very unstable, leading to the formation of a binuclear complex (5ClO4) with one bridging perchlorate anion, such that the copper(I) centers are four-coordinate. The same tendency is observed for the copper(II) bis(mu-hydroxo) compounds 6, which is additionally bridged by two perchlorate anions. Both copper(II) complexes 6 and 7 were obtained by molecular O2 oxidation of the corresponding copper(I) complexes. A comparison of the new copper(I) triphenylphosphine complexes 4ClO4 and 4PF6 with corresponding species obtained with the related tridentate ligands L1' and L1 (8ClO4 and 9, respectively) reveals surprisingly small differences in their spectroscopic properties. Density functional theory (DFT) calculations are used to shed light on the differences in bonding in these compounds and the spectral assignments. Finally, the reactivity of the different bis(pyrazolyl)methane complexes obtained here toward PPh3, CO, and O2 is discussed.     

Structural and kinetic study of reversible CO2 fixation by dicopper macrocyclic complexes. From intramolecular binding to self-assembly of molecular boxes

A study of the reversible CO2 fixation by a series of macrocyclic dicopper complexes is described. The dicopper macrocyclic complexes [Cu2(OH)2(Me2p)](CF3SO3)2, 1(CF3SO3)2, and [Cu2(mu-OH)2(Me2m)](CF3SO3)2, 2(CF3SO3)2, (Scheme 1) containing terminally bound and bridging hydroxide ligands, respectively, promote reversible inter- and intramolecular CO2 fixation that results in the formation of the carbonate complexes [{Cu2(Me2p)}2(mu-CO3)2](CF3SO3)4, 4(CF3SO3)4, and [Cu2(mu-CO3)(Me2m)](CF3SO3)2, 5(CF3SO3)2. Under a N2 atmosphere the complexes evolve CO2 and revert to the starting hydroxo complexes 1(CF3SO3)2 and 2(CF3SO3)2, a reaction the rate of which linearly depends on [H2O]. In the presence of water, attempts to crystallize 5(CF3SO3)2 afford [{Cu2(Me2m)(H2O)}2(mu-CO3)2](CF3SO3)4, 6(CF3SO3)4, which appears to rapidly convert to 5(CF3SO3)2 in acetonitrile solution. [Cu2(OH)2(H3m)]2+, 7, which contains a larger macrocyclic ligand, irreversibly reacts with atmospheric CO2 to generate cagelike [{Cu2(H3m)}2(mu-CO3)2](ClO4)4, 8(ClO4)4. However, addition of 1 equiv of HClO4 per Cu generates [Cu2(H3m)(CH3CN)4]4+ (3), and subsequent addition of Et3N under air reassembles 8. The carbonate complexes 4(CF3SO3)4, 5(CF3SO3)2, 6(CF3SO3)4, and 8(ClO4)4 have been characterized in the solid state by X-ray crystallography. This analysis reveals that 4(CF3SO3)4, 6(CF3SO3)4, and 8(ClO4)4 consist of self-assembled molecular boxes containing two macrocyclic dicopper complexes, bridged by CO32- ligands. The bridging mode of the carbonate ligand is anti-anti-mu-eta1:eta1 in 4(CF3SO3)4, anti-anti-mu-eta2:eta1 in 6(CF3SO3)4 and anti-anti-mu-eta2:eta2 in 5(CF3SO3)2 and 8(ClO4)4. Magnetic susceptibility measurements on 4(CF3SO3)4, 6(CF3SO3)4, and 8(ClO4)4 indicate that the carbonate ligands mediate antiferromagnetic coupling between each pair of bridged CuII ions (J = -23.1, -108.3, and -163.4 cm-1, respectively, H = -JS1S2). Detailed kinetic analyses of the reaction between carbon dioxide and the macrocyclic complexes 1(CF3SO3)2 and 2(CF3SO3)2 suggest that it is actually hydrogen carbonate formed in aqueous solution on dissolving CO2 that is responsible for the observed formation of the different carbonate complexes controlled by the binding mode of the hydroxy ligands. This study shows that CO2 fixation can be used as an on/off switch for the reversible self-assembly of supramolecular structures based on macrocyclic dicopper complexes.     

Self-assembly, structures, and solution dynamics of emissive silver metallacycles and helices

Reactions of 9,10-bis(diphenylphosphino)anthracene (PAnP) and AgX (X = OTf-, ClO4-, PF6-, and BF4-) led to luminescent Ag-PAnP complexes with rich structural diversity. Helical polymers [Ag(mu-PAnP)(CH3CN)X]n (X = OTf-, ClO4-, and PF6-) and discrete binuclear [Ag2(mu-PAnP)2(CH3CN)4](PF6)2, trinuclear [Ag3(mu-PAnP)3 supersetBF4](BF4)2, and tetranuclear [Ag4(mu-PAnP)4 superset(ClO4)2](ClO4)2 metallacycles were isolated from different solvents. The tri- and tetranuclear metallacycles exhibited novel puckered-ring and saddlelike structures. Variable-temperature (VT) 31P{1H}-NMR spectroscopy of the complexes was solvent dependent. The dynamics in CD3CN involve two species, but the exchange processes in CD2Cl2 are more complicated. A ring-opening polymerization was proposed for the exchange mechanism in CD3CN.     

Discrete and infinite 1D, 2D/3D cage frameworks with inclusion of anionic species and anion-exchange reactions of Ag3L2 type receptor with tetrahedral and octahedral anions

Complexes [PF6 subset(Ag3(titmb)2](PF6)2 (8) and {SbF6 subset[Ag3(titmb)2](SbF6)2}.H2O.1.5 CH3OH (9) are obtained by reaction of titmb and Ag+ salts with different anions (PF6(-) and SbF6(-)), and crystal structures reveal that they are both M3L2 cage complexes with short Ag...F interactions between the silver atoms and the fluorine atoms of the anions. In complex 8, a novel cage dimer is formed by weak Ag...F contacts; an unique cage tetramer formed via Ag...pi interactions (Ag...eta5-imidazole) between dimers and an infinite 1D cage chain is presented. However, each of the external non-disordered SbF6(-) anions connect with six cage 9s via Ag...F contacts, and each cage 9 in turn connects with three SbF6(-) anions to form a 2D network cage layer; and the layers are connected by pi-pi interactions to form a 3D network. The anion-exchange reactions of four Ag3L2 type complexes ([BF4 subset(Ag3(titmb)2](BF4)2 (6), [ClO4 subset(Ag3(titmb)2](ClO4)2 (7b), [PF6 subset(Ag3(titmb)2](PF6)2 (8) and [SbF6 subset(Ag3(titmb)2](SbF6)2.1.5CH3OH (9)) with tetrahedral and octahedral anions (ClO4(-), BF4(-), PF6(-) and SbF6(-)) are also reported. The anion-exchange experiments demonstrate that the anion selective order is SbF6(-) > PF6(-) > BF4(-), ClO4(-), and this anion receptor is preferred to trap octahedral and tetrahedral anions rather than linear or triangle anions; SbF6(-) is the biggest and most preferable one, so far. The dimensions of cage complexes with or without internal anions, anion-exchange reactions, cage assembly and anion inclusions, silver(I) coordination environments, Ag-F and Ag-pi interactions of Ag3L2 complexes 1-9 are discussed.     

Nickel(II) complexes with tetra- and pentadentate aminopyridine ligands: synthesis, structure, electrochemistry, and reduction to nickel(I) species

A series of nickel(II) complexes with polydentate aminopyridine ligands N,N,N'-tris-[2-(2'-pyridyl)ethyl]ethane-1,2-diamine (L1), N,N,N'-tris-[2-(2'-pyridyl)ethyl]-N'-methylethane-1,2-diamine (L2), and N,N'-bis-[2-(2'-pyridyl)ethyl]-N,N'-dimethylethane-1,2-diamine (L3) were synthesized and characterized by elemental analysis and spectroscopic methods. Single-crystal X-ray diffraction studies showed that the Ni(II) ions have five-coordinate square-pyramidal geometry in [NiL2](ClO(4))(2), similar to that previously found in [NiL1](ClO(4))(2) x CH(3)NO(2) (Hoskins, B. F.; Whillans, F. D.J. Chem. Soc., Dalton Trans. 1975, 657), and square-planar geometry in [NiL3](ClO(4))(2). All three nickel(II) complexes are reduced by sodium borohydride or sodium amalgam in organic solvents to nickel(I) species, which were identified by highly anisotropic EPR spectra at 100 K: g(1) = 2.239, g(2) = 2.199, and g(3) = 2.025 for [NiL1](+); g(axially) = 2.324 and g(radially) = 2.079 for [NiL2](+) and [NiL3](+). Cyclic voltammetry of the nickel(II) complexes in acetonitrile exhibited reversible reduction waves at -1.01 V for [NiL1](2+), -0.91 V for [NiL2](2+), and -0.83 V for [NiL3](2+) versus SCE, potentials which are significantly less negative than those of most previously characterized Ni(II) complexes with nitrogen-only donor atoms. Complexes [NiL1](2+) and [NiL2](2+) showed high catalytic activity in the electroreduction of 1,2-trans-dibromocyclohexane to cyclohexene.     

Preparation and oxygenation of (flavonolato)copper isoindoline complexes with relevance to quercetin dioxygenase

Mesitylcopper reacts with flavonol (flaH) in the presence of 1,3-bis(2-pyridylimino)isoindoline (indH) to yield the diamagnetic complex CuI(fla)(indH), which on reaction with molecular oxygen undergoes oxidative splitting of the C2-C3 bond of the pyranone ring of the flavonolate ligand to give CuI(indH)(O-bs) (O-bs = O-benzoylsalicylate) (orthorhombic, P1, a = 8.048(7) A, b = 8.969(9) A, c = 19.240(2) A, alpha = 85.69 degrees, beta = 80.24(7) degrees, gamma = 77.87(7) degrees, V = 1337(2) A3, Z = 2) and carbon monoxide. The reaction of [CuI(CH3CN)4]ClO4, flaH, and indH with dioxygen at room temperature affords the paramagnetic complex [CuII(fla)(indH)]ClO4 (mu = 2.10 mu B), and after elimination of HClO4, CuII(fla)(ind) (orthorhombic, Pbca, a = 8.888(2) A, b = 19.169(7) A, c = 33.614(10) A, alpha = beta = gamma = 90 degrees, V = 5727(3) A3, Z = 8) with mu = 1.86 mu B is formed. The latter undergoes cleavage of the pyranone ring on oxygenation at 80 degrees C to give CuII(ind)(O-bs) (mu = 1.87 mu B, nu(CO) = 1742 cm-1, and nu(CO2) = 1581, 1387 cm-1) and carbon monoxide. CuII(fla)(ind) and [CuII(fla)(indH)]ClO4 serve as good catalysts for the oxygenation of flavonol to O-benzoylsalicyclic acid.     

Synthesis and some first-row transition-metal complexes of the 1,2,4-triazole-based Bis(terdentate) ligands TsPMAT and PMAT

The employment of a strategy based on nucleophilic substitution, rather than Schiff base condensation, for the preparation of 1,2,4-triazole-based ligands has been investigated and has led to the synthesis of two new ligands, 4-amino-3,5-bis{[N-(2-pyridylmethyl)-N-(4-toluenesulfonyl)amino]methyl}-4H-1,2,4-triazole (TsPMAT, 14) and 4-amino-3,5-bis{[(2-pyridylmethyl)amino]methyl}-4H-1,2,4-triazole (PMAT, 15). These are the first examples of bis(terdentate) ligands incorporating the 1,2,4-triazole unit. TsPMAT (14) forms a dinuclear 2:2 complex with Co(BF4)2.6 H2O even when reacted in a metal-to-ligand molar ratio of 2:1. Similarly, the reaction of PMAT (15) with Mn(ClO4)2.6H2O or M(BF4)2.6 H2O (M=Fe, Co, Ni, Zn) in a ligand-to-metal molar ratio of 1:1 has afforded a series of complexes with the general formula [M(II) (2)(PMAT)2]X4. The metal centres in these complexes of TsPMAT (14) and PMAT (15) are encapsulated by two ligand molecules and doubly bridged by the N2 units of the 1,2,4-triazole moieties, which gives rise to N6 coordination spheres that are strongly distorted from octahedral, as evidenced by the X-ray crystal structure analyses of [Co(II) (2)(TsPMAT)(2)](BF(4))(4)6 MeCN (246 MeCN) and [Fe(II) 2(PMAT)2](BF4)4DMF (27DMF). Studies of the magnetic properties of [Co(II) 2(TsPMAT)2](BF4)4.4 H2O (244 H2O), [Mn(II) 2(PMAT)2](ClO4)4 (26), and [Co(II) 2(PMAT)2](BF4)4 (28) have revealed weak antiferromagnetic coupling (J=-3.3, -0.16, and -2.4 cm(-1), respectively) between the two metal centres in these complexes.     

Disilver(I) rectangular-shaped metallacycles: X-ray crystal structure and dynamic behavior in solution

Reaction of the ditopic semirigid ligand 1,2-bis(imidazolylmethyl)benzene (1,2-bImb) or the flexible ligand 1,4-bis(2-benzimidazolyl)butane (C4BIm) with AgX (X = ClO4-, BF4-, CF3CO2-) afforded five new complexes, namely, [Ag2(1,2-bImb)2](ClO4)2 (1), [Ag2(1,2-bImb)2](BF4)2 (2), [Ag2(1,2-bImb)2](CF3CO2)2.2CH3OH (3.2CH3OH), [Ag2(C4BIm)2](ClO4)2.2DMF (4.2DMF), and [Ag2(C4BIm)2](CF3CO2)2.2H2O (5.2H2O), all of which contain a centrosymmetric, rectangular-shaped cationic disilver(I) metallacycle [Ag2(L)2]2+. In 1-3, a pair of 1,2-bImb ligands takes on the syn conformation to connect two Ag(I) ions to give a compressed rectangle with a transannular Ag...Ag separation of 3.27-3.36 angstroms, whereas in 4 and 5, the pair of planar C4BIm ligands acts in the cis conformation to connect two Ag(I) ions to yield a normal rectangle with a transannular Ag...Ag separation of 7.67-7.91 angstroms. The anions form Ag...O or Ag...F weak interactions in 1-3 and O-H...O or N-H...O hydrogen bonds in 4 and 5 in crystal packing but exhibit no significant influence on the formation of the disilver(I) macrocycles. The solution structure and dynamic behavior of the complexes studied by electrospray ionization mass spectrometry, 1H NMR, and variable-temperature NMR indicated that the dynamic equilibrium between the [Ag2(L)2]2+ cation and the open-ring oligomers or other potential species occurs via solvent-assisted dissociative exchange. The metal-ligand exchange barrier was estimated to be 54.5 kJ mol(-1).