Synthesis and Structural Characterization of two Novel Copper(I) Complexes with Oxygen Donor

Two novel copper(I) complexes with Cu‐O bonds, [Cu₂L₂(PPh₃)₂](BF₄)₂ ( 1 ) and [Cu(L)(dppeo)](BF₄) ( 2 ) ( L = 6‐(4‐diethylmethylphosphonatephenyl)‐2,2′‐bipyridine, dppeo = bis(diphenylphosphino)ethane monoxide), have been prepared and their structures characterized. In the binuclear complex 1 , the ligand L serves as tridentate donor with the N, N′ and O as coordination atoms, and the two Cu^I atoms are bridged through both P = O donor atoms in different ligand L with a triphenylphosphine molecule as auxiliary ligand. While in mononuclear complex 2 , both ligands L and dppeo behave as bidentate with N^∧N from L and P^∧O from dppeo chelating to Cu^I atom.     

Novel Sesquiterpenoids from Siegesbeckia orientalis

Five new sesquiterpenoids, namely, 8β‐(angeloyloxy)‐4β,6α,15‐trihydroxy‐14‐oxoguaia‐9,11(13)‐dien‐12‐oic acid 12,6‐lactone ( 1 ), 4β,6α,15‐trihydroxy‐8β‐(isobutyryloxy)‐14‐oxoguaia‐9,11(13)‐dien‐12‐oic acid 12,6‐lactone ( 2 ), 11,12,13‐trinorguai‐6‐ene‐4β,10β‐diol ( 3 ), (1(10)E,4E,8Z)‐8‐(angeloyloxy)‐6α,15‐dihydroxy‐14‐oxogermacra‐(1(10),4,8,11(13)‐tetraen‐12‐oic acid 12,6‐lactone ( 9 ), and (1(10)E,4β)‐8β‐(angeloyloxy)‐6α,14,15‐trihydroxygermacra‐1(10),11(13)‐dien‐12‐oic acid 12,6‐lactone ( 11 ), and three new artifacts, (1(10)E,4Z)‐8β‐(angeloyloxy)‐9α‐ethoxy‐6α,15‐dihydroxy‐14‐oxogermacra‐1(10),4,11(13)‐trien‐12‐oic acid 12,6‐lactone ( 6 ), (1(10)E,4Z)‐8β‐(angeloyloxy)‐9α,13‐diethoxy‐6α,15‐dihydroxy‐14‐oxogermacra‐1(10),4‐dien‐12‐oic acid 12,6‐lactone ( 7 ), and (1(10)E,4Z)‐8β‐(angeloyloxy)‐9α‐ethoxy‐6α,15‐dihydroxy‐13‐methoxy‐14‐oxogermacra‐1(10),4‐dien‐12‐oic acid 12,6‐lactone ( 8 ), together with the three known sesquiterpenoids 4, 5 , and 10 , were isolated from the aerial parts of Siegesbeckia orientalis L. Their structures were established by spectral methods, especially 1D‐ and 2D‐NMR spectral methods.     

3D－QSAR Study on Diindolylmethane and Its Analogues with Comparative Molecular Field Analysis(CoMFA)

Comparative molecular field analysis (CoMFA),a three dimensional quantitative structure-activity relationship (3D-QSAR) method was applied to a series of diindolylmethane(DIM) analogs to study the relationship between their structure and their induction of CYP 1A1-associated ethoxyresorufin-O-deethylase(EROD) activity.A DISCO model of pharmacophore was derved to guide the superposition of the compounds.The coefficient of cross-validation (q^2) and non cross-validation(r^2) for the model established by the study are 0.827 and 0.988 respectively,the value of variance ratio (F) is 103.53 and standard error estimate (SEE)is 0.044.These values indicate that the CoMFA model derived is significant and might have a good prediction for the catalytic activity of DIM compounds.As a consequence,the predicted activity values of new designed compounds were all higher than that of the reported value.     

Heterotrimetallic 4f-3d coordination polymers: synthesis, crystal structure, and magnetic properties

A series of cyano-bridged heterotrimetallic complexes [CuL](2)Ln(H(2)O)(2)M(CN)(6).7H(2)O have been synthesized by the reactions of CuL (L(2)(-) = dianion of 1,4,8,11-tetraazacyclotradecane-2,3-dione), Ln(3+) (Ln = Gd or La), and [M(CN)(6)](3)(-) (M = Co, Fe, or Cr). X-ray diffraction analysis reveals that these complexes are isostructural and have a novel chain structure. The Ln(3+) ion is eight-coordinated by six oxygen atoms of two CuL and two water molecules and two nitrogen atoms of the bridging cyano ligands of two [M(CN)(6)](3)(-), while the [M(CN)(6)](3)(-) anion connects two Ln(3+) using two trans-CN(-) ligands giving rise to a chainlike structure. In the chain, every CuL group tilts toward the CN(-) ligand of adjacent [M(CN)(6)](3)(-) with the Cu-N(cyano) contacts ranging from 2.864(6) to 2.930(6) A. Magnetic studies on the CuGdCo complex (1) indicate the presence of ferromagnetic coupling between Cu(II) and Gd(III). The CuLaCr (5) and CuLaFe (2) complexes exhibit ferromagnetic interaction between paramagnetic Cu(II) and Cr(III)/Fe(III) ions through the weak cyano bridges (Cu-N(cyano) = 2.930(6) A for 2). A global ferromagnetic interaction is operative in the CuGdFe complex (3) with the concurrence of dominant ferromagnetic Cu(II)-Gd(III) and minor antiferromagnetic Gd(III)-Fe(III) as well as the ferromagnetic Cu(II)-Fe(III) interaction. For the CuGdCr complex (4), an overall antiferromagnetic behavior was observed, which is attributed to the presence of dominant antiferromagnetic Cr(III)-Gd(III) coupling and the minor ferromagnetic Cu(II)-Gd(III) and Cu(II)-Cr(III) interaction. Moreover, a spin frustration phenomenon was found in complex 4, which results from the ferro-ferro-antiferromagnetic exchanges in the trigonal Cu-Gd-Cr units. The magnetic susceptibilities of these complexes were simulated using suitable models. The magneto-structural correlation was investigated. These complexes did not show a magnetic phase transition down to 1.8 K.     

Synthesis of 1,3,4‐Oxadiazoles and 1,3‐Thiazolidinones Containing 1,4,5,6‐Tetrahydro‐6‐pyridazinone

The reaction of 1,4,5,6‐tetrahydro‐6‐pyridazinone‐3‐carboxylic acid hydrazides ( 1 ) with aromatic aldehydes afforded 1,4,5,6‐tetrahydro‐6‐pyridazinone‐3‐carbonyl aromatic aldehyde hydrazones ( 2a‐2g ). Heterocyclic derivatives linked 1,3,4‐oxadiazole obtained by cyclocondensation of 2a‐2g with acetic anhydride in absolute ethanol, and 2a‐2g cyclized with mercaptoacetic acid in DMF in the presence of anhydrous ZnCl₂ afforded the 1,3‐thiazolidinone derivatives. The structures of the new compounds were established by elemental analyses, IR, ¹H NMR and MS spectral data.     

A three‐dimensional lead(II) coordination polymer: poly[aqua‐μ‐imidazole‐4,5‐dicarboxyl­ato‐lead(II)]

In the title coordination polymer, [Pb(C₅H₂N₂O₄)(H₂O)]_n, the Pb^II atom is seven‐coordinated by one N atom and five O atoms from four individual imidazole‐4,5‐dicarboxyl­ate (HIDC²⁻) groups and one water mol­ecule. It is inter­esting to note that the HIDC²⁻ group serves as a bridging ligand to link the Pb^II atoms into a three‐dimensional microporous open‐framework.