Comparing a mononuclear Zn(II) complex with hydrogen bond donors with a dinuclear Zn(II) complex for catalysing phosphate ester cleavage

Introducing ligand based hydrogen bond donors to increase the activity of a mononuclear Zn(II) complex for catalysing phosphate ester cleavage can be a more effective strategy than making the dinuclear analogue.     

A diamagnetic dititanium(III) paddlewheel complex with no direct metal-metal bond

Reaction of Ti[N(But)Ar]3 (Ar = 3,5-C6H3Me2 or Ar' = C6H5) with CO2 at -40 degrees C produces diamagmetic Ti(III) paddlewheel complexes with long Ti-Ti separations (>3.4 Angstrom), thus excluding direct Ti-Ti bonding. 1H NMR spectroscopy shows that the compounds are diamagnetic in solution in the temperature range of -65 to +70 degrees C. In the solid state, the diamagnetism was found to persist between 2 and 300 K. Calculations at the density functional theory level suggest that the diamagnetism results from antiferromagnetic coupling by superexchange through the ligand pi system.     

Reactivity of mononuclear alkylperoxo copper(II) complex. O-O bond cleavage and C-H bond activation

A detailed reactivity study has been carried out for the first time on a new mononuclear alkylperoxo copper(II) complex, which is generated by the reaction of copper(II) complex supported by the bis(pyridylmethyl)amine tridentate ligand containing a phenyl group at the 6-position of the pyridine donor groups and cumene hydroperoxide (CmOOH) in CH3CN. The cumylperoxo copper(II) complex thus obtained has been found to undergo homolytic cleavage of the O-O bond and induce C-H bond activation of exogenous substrates, providing important insights into the catalytic mechanism of copper monooxygenases.     

A wine red copper(II) complex of a tetradentate nitrogen donor showing two-electron oxidation. Generation of a copper(II)-phosphine bond

Using the 1 : 2 condensate of benzil and 2-hydrazinopyridine as the ligand LH₂ (H: dissociable NH proton), the red complex Cu(LH₂)(ClO₄)₂ (1) was synthesized. The ligand also afforded the orange [Zn(LH₂)(OH₂)₂](ClO₄)₂ (2). The X-ray crystal structures of the ligand, 1 and 2 have been determined. The metals in 1 and 2 have octahedral N₄O₂ environments. 1 is paramagnetic with μ_eff of one unpaired electron (1.63 μ_B and displays an axial EPR spectrum in the solid state with <g> = 2.07, characteristic of a (d_x2_?y2)¹ ground state (g_|| > g_⊥; A_|| = 16 mT). In cyclic voltammetry, 1 displays a two-electron oxidation around 0.9 V versus NHE. The two-electron oxidized (coulometrically) solution of 1 (golden yellow) gives an EPR spectrum with <g> = 2.17 and g_|| < g_⊥. The reaction of PPh₃ with 1 yields the orange complex [Cu(LH₂)(PPh₃)](ClO₄)₂ (4). With the assumed chemical formula, the effective magnetization of 4 corresponds to one electron. Its EPR spectrum in the solid state is isotropic with g = 2.07. This g value yields a theoretical μ_eff of 1.80 μ_B at 298 K from Curie’s law, which matches very well with the experimental value of 1.89 μ_B at room temperature. Since single crystals of 4 could not be obtained, DFT calculations at the UBP86/6–311G(2d,p) level have been carried out and indicate that the cation in 4 is square pyramidal with the phosphine at the apex. The ease of the oxidation of the metal in 1 leads to the stabilization of the rare Cu(II)-P bond in 4.     

(p-Cymene)thioglycollatoruthenium(II) dimer; a complex with an ambi-basic S,O-donor ligand

The title compound was prepared from the (p-cymene)ruthenium chloride dimer and thioglycollic acid. The structure is a centrosymmetric dimer bridged by the soft-base S atoms, with the hard-base O atoms of the carboxylate group chelating to form a five-membered twisted-ring. The coordination of the ruthenium atoms is completed by a η⁶-p-cymene ligand, giving an 18-electron count. The Ru–S bonds are essentially equal at 2.396(1) Å.     

A weak,short metal-metal bond in a chromium(II) amidinate complex

Treatment of chromium(II) chloride with 2 equiv of Li[tBuNC(CH3)NtBu], Li[iPrNC(CH3)NiPr], or Li[tBuNC(CH3)NEt] (prepared from the corresponding carbodiimides and methyllithium) afforded Cr[tBuNC(CH3)NtBu]2 (1, 50%), Cr[iPrNC(CH3)NiPr]2 (2, 54%), and [Cr(tBuNC(CH3)NEt)2]2 (3, 58%) as deep blue, purple, and amber or metallic green crystals, respectively. Cr[tBuNC(CH3)NtBu]2 and Cr[iPrNC(CH3)NiPr]2 possess monomeric structures in the solid state with tetrahedral and square planar geometries about the chromium centers, respectively. [Cr(tBuNC(CH3)NEt)2]2 exists as a dimer in the solid state, with two mu2-amidinate ligands, two eta2-amidinate ligands, and a chromium-chromium bond length of 1.9601(12) A. [Cr(tBuNC(CH3)NEt)2]2 is diamagnetic in the solid state, as determined by magnetic susceptibility measurement and CP/MAS 13C NMR spectroscopy. However, [Cr(tBuNC(CH3)NEt)2]2 dissociates into paramagnetic monomers in solution, as determined by observation of extremely broad peaks in the 1H NMR spectra in cyclohexane-d12 and benzene-d6, a solution magnetic moment measurement, and by solution molecular weight measurements in benzene. The combined results suggest that the chromium-chromium bond strength in [Cr(tBuNC(CH3)NEt)2]2 is weak and cannot exceed the difference in solvation energies between the dimer and two monomers, plus any increase in metal-nitrogen bond strengths in the monomers.     

Efficient plasmid DNA cleavage by a mononuclear copper(II) complex

The Cu(II) complex of the ligand all-cis-2,4,6-triamino-1,3,5-trihydroxycyclohexane (TACI) is a very efficient catalyst of the cleavage of plasmid DNA in the absence of any added cofactor. The maximum rate of degradation of the supercoiled plasmid DNA form, obtained at pH 8.1 and 37 degrees C, in the presence of 48 microM TACI.Cu(II), is 2.3 x 10(-3) s(-1), corresponding to a half-life time of only 5 min for the cleavage of form I (supercoiled) to form II (relaxed circular). The dependence of the rate of plasmid DNA cleavage from the TACI.Cu(II) complex concentration follows an unusual and very narrow bell-like profile, which suggests an high DNA affinity of the complexes but also a great tendency to form unreactive dimers. The reactivity of the TACI.Cu(II) complexes is not affected by the presence of several scavengers for reactive oxygen species or when measured under anaerobic conditions. Moreover, no degradation of the radical reporter Rhodamine B is observed in the presence of such complexes. These results are consistent with the operation of a prevailing hydrolytic pathway under the normal conditions used, although the failure to obtain enzymatic religation of the linearized DNA does not allow one to rule out the occurrence of a nonhydrolytic oxygen-independent cleavage. A concurrent oxidative mechanism becomes competitive upon addition of reductants or in the presence of high levels of molecular oxygen: under such conditions, in fact, a remarkable increase in the rate of DNA cleavage is observed.     

Metal complexes with pyridone-based radicals: Preparation and properties of a dinuclear paddle-wheel copper(II) complex and a mononuclear palladium(II) complex

We prepared and characterized dinuclear copper(II) and mononuclear palladium(II) complexes coordinated with a pyridine-based open-shell ligand, 5-(4′,4′,5′,5′-tetramethylimidazoline-3′-oxide-1′-oxyl)-2(1H)-pyridone (=HL). In the copper(II) dinuclear complex [Cu₂(L)₄(DMF)₂] (1), four deprotonated ligands are coordinated as bridging ligands to form a paddle-wheel type unit. In the palladium(II) complex trans-[PdCl₂(HL)₂] (2), two HL ligands in the neutral hydroxypyridine form are coordinated to the trans positions of the metal ion via the nitrogen atoms. The hydroxyl groups of the ligands are hydrogen-bonded to the chlorine atoms of neighboring molecules, thereby creating a hydrogen-bonded double-chain molecular arrangement. Magnetic susceptibilities of these complexes were measured and analyzed. The small intramolecular antiferromagnetic interaction in the latter complex may originate from superexchange through the diamagnetic metal center.     

Self-activated DNA cleavage of a water-soluble mononuclear Cu(II) complex with polyquinolinyl ligand

The synthesis and characterization of a water-soluble mononuclear Cu(II) complex, [CuLCl₂]·2CH₃CH₂OH, where L = bis(2-quinolinyl methyl)benzyl-amine has been reported. L is a tridentate polyquinolinyl ligand, coordinated to Cu(II) via NNN donors. The central copper ion of 1 has N₃Cl₂ donor set in a distorted trigonal-bipyramidal geometry. The dimer existing in the solid state resulted from hydrogen bonds and π–π accumulation between two mononuclear units. The interaction of 1 with CT-DNA has been explored by absorption and emission titration methods, revealing partial intercalation between 1 and CT-DNA. Moreover, 1 could make pBR322 plasmid DNA cleaved by a self-activated oxidative process; hydroxyl radical and singlet oxygen may be the main reactive oxygen species species in the process. Complex 1 may quench the intrinsic fluorescence of bovine serum albumin in a static quenching process, which has been investigated by UV–visible and fluorescence spectroscopic methods. 1 also demonstrates potent cytotoxity against Hela cells with IC₅₀ value of 2.84 μM, which shows it to be a potential candidate as an anticancer metal-based drug.     

Disulfide bond cleavage induced by a platinum(II) methionine complex

The cleavage of a disulfide bond and the redox equilibrium of thiol/disulfide are strongly related to the levels of glutathione (GSH)/oxidized glutathione (GSSG) or mixed disulfides in vivo. In this work, the cleavage of a disulfide bond in GSSG induced by a platinum(II) complex [Pt(Met)Cl2] (where Met = methionine) was studied and the cleavage fragments or their platinated adducts were identified by means of electrospray mass spectrometry, high-performance liquid chromatography, and ultraviolet techniques. The second-order rate constant for the reaction between [Pt(Met)Cl2] and GSSG was determined to be 0.4 M(-1) s(-1) at 310 K and pH 7.4, which is 100- and 12-fold faster than those of cisplatin and its monoaqua species, respectively. Different complexes were formed in the reaction of [Pt(Met)Cl2] with GSSG, mainly mono- and dinuclear platinum complexes with the cleavage fragments of GSSG. This study demonstrated that [Pt(Met)Cl2] can promote the cleavage of disulfide bonds. The mechanistic insight obtained from this study may provide a deeper understanding on the potential involvement of platinum complexes in the intracellular GSH/GSSG systems.     

Synthesis, structure and DFT study of a pyrazolate stabilized mononuclear Rh(II) complex

Reaction of 3,5-(CF(3))(2)PzLi with anhydrous RhCl(3) in THF gives [Li(THF)](2)Rh(μ-3,5-(CF(3))(2)Pz)(4) (1) as a rare example of a mononuclear, paramagnetic Rh(II) complex (Pz = pyrazolate).     

Magnetic properties of a mononuclear iron(II) complex with a typical FeN6 coordination octahedron

A mononuclear iron(II) complex with the tripodal ligand bis(pyridin‐2‐ylmethyl)(quinolin‐2‐ylmethyl)amine (dpqa) has been synthesized and structurally characterized, namely [bis(pyridin‐2‐ylmethyl)(quinolin‐2‐ylmethyl)amine‐κ⁴N,N′,N′′,N′′′]bis(thiocyanato‐κS)iron(II), [Fe(NCS)₂(C₂₂H₂₀N₄)], exhibits a three‐dimensional supramolecular network viaπ–π interactions and S...H—C hydrogen‐bonding interactions between adjacent Fe^II centres. Temperature‐dependent magnetic measurements under different external pressures and X‐ray diffraction measurements indicate that all the Fe^II centres in this complex retain a high‐spin state upon cooling from 300 to 2 K. The surprising absence of spin‐crossover behaviour for this mononuclear iron(II) complex is attributed to the steric hindrance originating from the substituted quinoline ring in the dpqa ligand.     

Self-promoted electron transfer from cobalt(II) porphyrin to p-fluoranil to produce a dimer radical anion-cobalt(III) porphyrin complex

Self-promoted electron transfer from a cobalt(II) porphyrin [Co(II)OEP] to p-fluoranil (F4Q) occurs, exhibiting a second-order dependence of the electron-transfer rate with respect to the F4Q concentration due to the formation of a strong complex between the dimer radical anion [(F4Q)2*-] and the resulting Co(III)OEP+.     

From a trinuclear platinum(III) phosphido derivative to a platinum(II) cluster: formation of a P-C bond

Reaction of the trinuclear Pt(III)-Pt(III)-Pt(II) [(C6F5)2Pt(III)(mu-PPh2)2Pt(III)(mu-PPh2)2Pt(C6F5)2] (2) derivative with NBu4Br or NBu4I results in the formation of the trinuclear Pt(II) complexes [NBu4][(PPh2C6F5)(C6F5)Pt(mu-PPh2)(mu-X)Pt(mu-PPh2)2Pt(C6F5)2] [X = I (3), Br (4)] through an intramolecular PPh2/C6F5 reductive coupling and the formation of the phosphine PPh2C6F5. The trinuclear Pt(II) complex [(PPh2C6F5)(C6F5)Pt(mu-PPh2)Pt(mu-PPh2)2Pt(C6F5)2] (5), which displays two Pt-Pt bonds, can be obtained either by halide abstraction in 4 or by refluxing of 2 in CH2Cl2. This latter process also implies an intramolecular PPh2/C6F5 reductive coupling. Treatment of complex 5 with several ligands (Br-, H-, and CO) results in the incorporation of the ligand to the cluster and elimination of one (X = H-) or both (X = Br-, CO) Pt-Pt bonds, forming the trinuclear complexes [NBu4][(PPh2C6F5)(C6F5)Pt(mu-PPh2)(mu-X)Pt(mu-PPh2)2Pt(C6F5)2] [X = Br (6), H (7)] or [(PPh2C6F5)(C6F5)Pt(mu-PPh2)2Pt(mu-PPh2)(CO)Pt(C6F5)2(CO)] (8). The structures of the complexes have been established on the basis of 1H, 19F, and 31P NMR data, and the X-ray structures of the complexes 2, 3, 5, and 7 have been established. The chemical relationship between the different complexes has also been studied.     

High frequency electron paramagnetic resonance (HFEPR) study of a high spin Co(II) complex

Variable high-frequency electron paramagnetic resonance data were collected for a single crystal of [Zn(hmp)(dmb)Cl]₄ (1) doped with a small quantity of high spin Co(II), where dmb is 3,3-dimethyl-1-butanol and hmp- is the monoanion of 2-hydroxy-methylpyridine. The lack of solvent in the lattice of complex 1 results in very little disorder. Consequently, the EPR spectra are extremely sharp, enabling precise comparisons with theoretical simulations. We find the ground state of the Co(II) ions to be an effective spin S′ = 1/2 Kramers’ doublet with a highly anisotropic g-tensor. The anisotropy is found to be of the easy-axis type, with the single-ion easy axis directions tilted away from the crystallographic c direction by 58°.     

Linear, high molecular weight polyethylene from a discrete, mononuclear phosphinoarenesulfonate complex of nickel(II)

A well-defined, homogeneous catalyst, [(Ph)(2-(2',6'-(OMe)(2)-C(6)H(3))-C(6)H(4))P(2-SO(3)-C(6)H(4))]Ni(Ph)PPh(3), in which a single, bulky ortho-biphenyl substituent on the chelating phosphine blocks one axial position, is very active for formation of linear polyethylene (M(n) = 403,000 g mol(-1), M(w)/M(n) = 1.87).     

Magnetic ordering in a mononuclear cobalt(II) complex containing a Schiff-base pentadentate ligand

A mononuclear cobalt(II) complex CoL5, containing the pentadentate O2N3 salen-type Schiff-base ligand H2L5=N,N[prime or minute]-bis(3-tert-butyl-2-hydroxy-5-methylbenzylidenyl)-1,7-diamino-4-methyl-4-azaheptane, exhibits magnetic ordering at 4 K as proven by ac magnetic susceptibility (both in- and out-of-phase), magnetization, field-cooled magnetization and zero-field cooled magnetization measurements.