The effect of anions in the synthesis and structure of pyrazolylamidino copper(II) complexes.

Six new pyrazolylamidino Cu(II) complexes are synthesized directly from the reactions of Cu(X)2 salts (X = ClO4-, BF4-, or Cl-) and pyrazole (pzH) in nitrile solution (RCN, R = Me or Et) at 298 K via the metal-mediated coupling of RCN with pzH: [Cu(HNC(R)pz)2(X)2] (X = ClO4- or BF4-, R = Me, 1 or 7 and Et, 2 or 8, respectively) and dichloro Cu(II) complexes [Cu2Cl2(µ-Cl)2(HNC(Me)pz)2] (3) and [CuCl2(HNC(Et)pz)] (4). Four more new complexes, [Cu2(µ-Cl)2(HNC(Me)pz)2(pzH)2][X]2 (X = ClO4-, 5 and BF4-, 9) and [Cu2(µ-Cl)2(HNC(Et)pz)2(pzH)2(X)2] (X = ClO4-, 6 and BF4-, 10), are obtained indirectly from the anion substitution reaction with Cl- ions in 1 and 7, and 2 and 8, respectively. All complexes are characterized by EA, FTIR, UV-vis and EPR spectroscopy and X-ray crystallographic analyses. HNC(Et)pz or pzH is unobserved in both the nitrile-exchange reaction of 2 to d6-1 and the anion-substitution reaction of 2 to d6-5 in the CD3CN solution. The 1H NMR results reveal that the pzH-RCN coupling is intramolecular and reversible on a Cu(II) center. The crystal structures of these complexes show diverse supramolecular assemblies through imino NH⋯anion hydrogen bonds and pyrazolylamidino pz-pz (π⋯π) and pz-Cu(II) (π⋯metal) interactions. EPR results suggest weak magnetic couplings between Cu(II) centers in the polynuclear Cu(II) complexes. The yield and rate of the formation of 1 are higher in the reaction of Cu(ClO4)2 with a 4-fold molar excess of pzH compared with a 2-fold excess, indicating that [Cu(pzH)4]2+ is the more active species for pzH-RCN coupling. The highest rate for the formation of 1 is achieved when [Cu(pzH)4(ClO4)2] is used in MeCN solution. Thus, a plausible synthetic path for synthesizing pyrazolylamidino Cu(II) complexes is established. An intermediate species, [Cu(HNC(Me)pz)2(pzH)2][ClO4]2 (1a), is proposed for the synthetic process based on spectroscopic studies and DFT calculations. The reaction of [Cu(pzH)4X2] (X = ClO4-, Cl-, NO3-, or BF4-) in MeCN solution suggests that the lability of coordinated anions upon nitrile substitution affects the rate of the formation of bis-pyrazolylamidino Cu(II) complexes.

Catalytic O2 activation toward oxidative N-S bond formation by a thiolato Fe(III) complex.

Compounds with the benzisothiazol-3-one (BIT) skeleton perform excellently in the pharmaceutical field, although current synthetic methods remain limited in terms of synthetic efficiency. Herein, we report the catalytic intramolecular N-S bond formation for BITs from easily prepared disulfide precursors by an Fe(III) dithiolate through O2 activation at 298 K. Interestingly, the catalytic performance is enhanced by substituting O2 with a milder O-donor oxidant, ONMe3. Catalytic oxygenation of PPh3 to OPPh3 can also proceed under similar conditions. In addition, the first anionic monosulfenato Fe(III) species, Fe(III)-S(O)R, is isolated with structural characterization from the reaction of Fe(III) thiolate and ONMe3.

Demethylation of an artificial hydrogenase agent for prolonged CO release and enhanced anti-tau aggregation activity.

Carbon monoxide (CO) plays an important role in signaling in cells, making its use as a therapeutic tool highly intriguing. Reduced burst emissions are important to avoid the cytotoxicity and tissue damage caused by CO. Here, we developed a stable diiron carbonyl [FeFe] hydrogenase agent that enables prolonged CO release activity (half-life of over 9 h) in cells. The integrated analysis allowed the identification of the key intermediate sites and CO accumulations with subcellular resolution. We observed that the [FeFe]A complex was enriched in neurons with S-methyl bond rupture. Furthermore, the [FeFe]A complex efficiently reduced the aggregation of tau proteins (49.3% reduction) and showed superior biocompatibility in nerve cells (∼ 95% survival).

Genome-wide analysis of cervical secretions obtained during embryo transfer reveals the association between deoxyribonucleic acid methylation and pregnancy outcomes.

OBJECTIVE: To study whether the methylation status of cervical secretions can reflect the ability of the endometrium to allow embryo implantation. DESIGN: Case-control study. SETTING: In vitro fertilization centers. PATIENT(S): Women undergoing embryo transfer cycles, in which at least 1 good-quality embryo was transferred. INTERVENTION(S): Collection of cervical secretions during the procedure of embryo transfer. MAIN OUTCOME MEASURE(S): Methylation profiles of cervical secretions in relation to pregnancy outcomes. RESULT(S): Genome-wide methylation profiles differ between cervical secretions from pregnancy and nonpregnancy cycles. Clustering analysis on the basis of the top 2,000 differentially methylated probes of cervical secretions from 28 pregnancy and 29 nonpregnancy cycles correctly categorized 86.0% of the samples in terms of conceptional status, which was verified in selected genes by quantitative methylation-specific polymerase chain reaction and validated in another independent sample set. The combination of selected genes was estimated to predict pregnancy outcomes with a maximal area under the receiver operating characteristic curve of 0.83. CONCLUSION(S): The methylation profiles of cervical secretions were associated with pregnancy outcomes in embryo transfer cycles. Although not clinically useful at present, deoxyribonucleic acid methylation in cervical secretions may shed new light on the less invasive assessment of endometrial receptivity.

High-Frequency Fe-H and Fe-H2 Modes in a trans-Fe(η2-H2)(H) Complex: A Speed Record for Nuclear Resonance Vibrational Spectroscopy.

Nuclear resonance vibrational spectroscopy (NRVS) and density functional theory (DFT) are complementary tools for studying the vibrational and geometric structures of specific isotopically labeled molecular systems. Here we apply NRVS and DFT to characterize the trans-[57Fe(η2-H2)(H)(dppe)2][BPh4] [dppe = 1,2-bis(diphenylphosphino)ethane] complex. Heretofore, most NRVS observations have centered on the spectral region below 1000 cm-1, where the 57Fe signal is strongest. In this work, we show that state-of-the-art synchrotron facilities can extend the observable region to 2000 cm-1 and likely beyond, in measurements that require less than 1 day. The 57Fe-H stretch was revealed at 1915 cm-1, along with the asymmetric 57Fe-H2 stretch at 1774 cm-1. For a small fraction of the H2-dissociated product, the 57Fe-H stretch was detected at 1956 cm-1. The unique sensitivity to 57Fe motion and the isolated nature of the Fe-H/H2 stretching modes enabled NRVS to quantitatively analyze the sample composition.

Dioxygen activation by a dinuclear thiolate-ligated Fe(ii) complex.

Dioxygen activation by FeII thiolate complexes is relatively rare in biological and chemical systems because the sulfur site is at least as vulnerable as the iron site to oxidative modification. O2 activation by FeII-SR complexes with thiolate bound trans to the O2 binding site generally affords the FeIV[double bond, length as m-dash]O intermediate and oxidized thiolate. On the other hand, O2 activation by Fe(ii)-SR complexes with thiolate bound cis to the O2 binding site generates FeIII-O-FeIII or S-oxygenated complexes. The postulated FeIV[double bond, length as m-dash]O intermediate has only been identified in isopenicillin N synthase recently. We demonstrated here that O2 activation by a dinuclear FeII thiolate-rich complex produces a mononuclear FeIII complex and water with a supply of electron donors. The thiolate is bound cis to the postulated dioxygen binding site, and no FeIII-O-FeIII or S-oxygenated complex was observed. Although we have not detected the transient intermediate by spectroscopic measurements, the FeIV[double bond, length as m-dash]O intermediate is suggested to exist by theoretical calculation, and P-oxidation and hydride-transfer experiments. In addition, an unprecedented FeIII-O2-FeIII complex supported by thiolates was observed during the reaction by using a coldspray ionization time-of-flight mass (CSI-TOF MS) instrument. This is also supported by low-temperature UV-vis measurements. The intramolecular NHO[double bond, length as m-dash]FeIV hydrogen bonding, calculated by DFT, probably fine tunes the O2-activation process for intramolecular hydrogen abstraction, avoiding the S-oxygenation at cis-thiolate.

Crystal Structure Analysis of the Repair of Iron Centers Protein YtfE and Its Interaction with NO.

Molecular mechanisms underlying the repair of nitrosylated [Fe-S] clusters by the microbial protein YtfE remain poorly understood. The X-ray crystal structure of YtfE, in combination with EPR, magnetic circular dichroism (MCD), UV, and (17) O-labeling electron spin echo envelope modulation measurements, show that each iron of the oxo-bridged Fe(II) -Fe(III) diiron core is coordinatively unsaturated with each iron bound to two bridging carboxylates and two terminal histidines in addition to an oxo-bridge. Structural analysis reveals that there are two solvent-accessible tunnels, both of which converge to the diiron center and are critical for capturing substrates. The reactivity of the reduced-form Fe(II) -Fe(II) YtfE toward nitric oxide demonstrates that the prerequisite for N2 O production requires the two iron sites to be nitrosylated simultaneously. Specifically, the nitrosylation of the two iron sites prior to their reductive coupling to produce N2 O is cooperative. This result suggests that, in addition to any repair of iron centers (RIC) activity, YtfE acts as an NO-trapping scavenger to promote the NO to N2 O transformation under low NO flux, which precedes nitrosative stress.

A dinitrosyliron complex within the homoleptic Fe(NO)4 anion: NO as nitroxyl and nitrosyl ligands within a single structure.

Nitrosylation of the chelate-thiolate-containing dinitrosyliron complex (DNIC) [(S(CH(2))(3)S)Fe(NO)(2)](-) triggers nitric oxide (NO) activation to generate the homoleptic nitrosyl {Fe(NO)(2)}(9) DNIC [Fe(NO)(4)](-) (1) made up of two nitroxyls (or two NO anions) attached to a delocalized {Fe(NO)(2)}(9) motif. The significantly longer N3-O3/N4-O4 [1.380(12) and 1.280(12) Å] and Fe1-N3/Fe1-N4 [2.008(11) and 2.045(10) Ǻ] bond distances reflect that N3-O3 and N4-O4 of complex 1 may act as the nitroxyl-coordinated ligands. That is, the electronic structure of the DNIC 1 is best described as a {Fe(NO)(2)}(9) motif coordinated by two nitroxyl (NO(-)) ligands.

N-[2-(Methyl-sulfan-yl)phen-yl]-2-sulfanylbenzamide.

In the title compound, C(14)H(13)NOS(2), the S atom with the methyl group is involved in an intra-molecular hydrogen bond with the amido H atom. In the crystal, the sulfanyl H atoms form inter-molecular hydrogen bonds with the O atoms, connecting the mol-ecules into zigzag chains along the c axis. The two aromatic rings exhibit a small interplanar angle of 16.03 (9)°.

Selective encapsulation of volatile and reactive methyl iodide.

A simple organic molecular container can selectively encapsulate the volatile and highly reactive MeI through hydrogen-bonding interactions in solution. The remarkable encapsulation of MeI without self-methylation of the container appears to be determined by the complementary binding sites and the rigidity of the hydrogen-bonding array constrained by the molecular framework.

N,N'-Bis[(1H-imidazol-1-yl)meth-yl]-2,2'-(disulfanedi-yl)dianiline.

The symmetrical title compound, C(20)H(20)N(6)S(2), contains a disulfide bond of 2.0884 (6) Å. The C-S-S-C torsion angle is -59.57 (7)°. In the crystal, classical N-H⋯N and non-classical C-H⋯N hydrogen bonds link the compounds into chains along the a axis.

Assembly and disassembly of a Zn10 high-nuclearity circular helicate.

A nano-scale decanuclear Zn(II) circular helicate is synthesized without the aid of counteranions during the assembly process, and can be totally disassembled into its reactants by specific anions.

Selective capture of volatile iodine using amorphous molecular organic solids.

A simple shape-persistent organic molecular container is capable of selective absorption and storage of I(2(g)) over water vapor and NO gas even in its amorphous solid state. In addition, the strongly associated I(2) can be efficiently released from the charged container in organic solvents under ambient conditions.

trans-Diacetonitrile-tetra-kis(1H-pyrazole-κN)nickel(II) dinitrate.

In the title complex, [Ni(CH(3)CN)(2)(C(3)H(4)N(2))(4)](NO(3))(2), the cation lies on an inversion center and adopts an octa-hedral coordination geometry about the Ni atom. The two acetonitrile ligands are in a trans conformation. N-H⋯O hydrogen bonds between cations and anions link the complex mol-ecules into one-dimensional chains running parallel to [100].