Codimerization of quadricyclane withendo,exo-hexacyclo[9.2.1.02,10.03,8.04,6.05,9]tetradec-12-ene catalyzed by the Pd(PPh3)4 complex

endo,exo-Hexacyclo[9.2.0^2,10.0^3,8.0^4,6.0^5,9]tetradec-12-ene (1) undergoes cyclocodimerization with quadricyclane (Q) in the presence of the Pd(PPh₃)₄ complex to giveexo,exo,endo,exo-decacyclo[9.9.1.0^2,10.0^3,8.0^4,6.0^5,9.0^12,20.0^13,18.0^14,16.0^15,19]heneicosane (2) andendo,exo,endo,exo-decacyclo[9.9.1.0^2,10.0^3,8.0^4,6.0^5,9.0^12,20.0^13,18.0^14,16.0^15,19]heneicosane (3) in a ratio of 10 7 (yield up to 26 %). Simultaneously, homocyclotrimerization of Q occurs to give three known C₂₁ hydrocarbons (4–6). The yields of compounds2 and3 and the selectivity of the process depend considerably on the reaction conditions and the molar ratio of1 and Q. Compounds2 and3 that were obtained were characterized by¹³C NMR spectra.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 11, pp. 1983–1985, November, 1994.     

Formation of polycyclic hydrocarbons containing a spiropentane or methylenecyclobutane moiety upon thermal decomposition of cyclopropane-containing 1-pyrazolines

1-Pyrazolines1 and2 obtained by 1,3-dipolar cycloaddition of diazocyclopropane to norbornene or deltacyclene undergo dediazotization at 410–450°C to give a mixture of strained hydrocarbons, namely, spirocyclopropane-1,3'-tricyclo[3.2.1.0^2,4]octane (4) or spiro{cyclopropane-1,4'-pentacyclo[4.4.0.0^2,8.0^3,5.0^7,9]decane} (6) and isomeric tricyclo[5.2.1.0^2,5]dec-5-enes (5) or pentacyclo[6.4.0.0^2,10.0^3,6.0^9,11]dec-6-enes (7) in a 30–70% overall yield. An increase in temperature favors the isomerization of spiro hydrocarbons4 and6 to the respective unsaturated hydrocarbons5 and7. The latter undergo cyclopropanation with diazomethane in the presence of Pd(acac)₂ or (PhO)₃P · CuCl to afford polycyclanes9a,b or10a,b containing a spiro[2.3]hexane moiety condensed at thecis-1,4 position. Unsaturated 1-pyrazoline3 obtained from diazocyclopropane and norbornadiene decomposes at 330–370°C with elimination of cyclopentadiene to give 3(5)-vinylpyrazole in a yield up to 75%.Some of the results reported in this paper have been presented at the VIIIth European Symposium on organic chemistry (Barcelona, August–September 1993),cf. Ref. 1.Translated fromIzyestiya Akademii Nauk. Seriya Khimicheskaya, No. 4, pp. 662–667, April, 1994.This study was financially supported by the Russian Fund for Fundamental Research (grant 94-03-08902).     

One-Pot Synthesis of Cage-Functionalized,Ketal-Containing Crown Ethers

Acid-catalyzed reaction of pentacyclo[5.4.0.0^2,6.0^3,10.0^5.9]undecane-8,11-dione (1) with penta(ethylene glycol) produced two cage-functionalized, ketal-containing crown ethers, i.e., 2 and 3, in low yield. The structure of 2 was established unequivocally by direct methods. Alkali metal picrate extraction data obtained for 2 and for a structurally related model compound, i.e., 18-crown-6,indicate that 2 is an inefficient alkali metal picrate extracting agent.     

Synthesis and spectral properties of substituted 4-chlorooxazoloquinolines

Summary The treatment of a mixture of linearly and angularly annelated 2-substituted oxazolo[4,5-f]quinolones (5a–c) and oxazolo[5,4-g]quinolones (6a–c) and similarly the treatment of 2-substituted oxazolo[5,4-f]quinolones (7a–c) and oxazolo[4,5-g]quinolones (8b,c) with POCl₃ afforded substituted 4-chlorooxazolo[4,5-f]quinolines (9a–c) and 2-substituted 4-chlorooxazolo[5,4-f]quinolines (10b,c), respectively. Spectral characteristics of the synthesized derivatives (¹H and¹³C NMR, IR, UV, and MS) are discussed.Dedicated to Prof.Fritz Sauter on the occasion of his 65th birthday     

氨基喹啉水杨醛Schiff碱配合物的合成、晶体结构及抑菌性能

经缩合反应制备了4-甲氧基水杨醛缩-6-氨基喹啉希夫碱配体(L),并采用溶剂热法使其与Co(Ⅱ)、Zn(Ⅱ)和Cu(Ⅱ)三种金属离子进行配位得到配合物[Co L2](1),[ZnL_2](2)及[Cu L2](3),所得化合物结构通过元素分析、红外光谱、核磁共振谱及X射线单晶衍射法进行表征。生物测试结果表明,配体(L)及配合物1~3对马铃薯干腐病菌、苹果炭疽病菌、苹果腐烂病菌、番茄灰霉病菌4种植物病原菌具有较好的抑菌活性。     

氨基喹啉水杨醛Schiff碱配合物的合成、晶体结构及抑菌性能

经缩合反应制备了4-甲氧基水杨醛缩-6-氨基喹啉希夫碱配体（L）,并采用溶剂热法使其与Co（Ⅱ）、Zn（Ⅱ）和Cu（Ⅱ）三种金属离子进行配位得到配合物[CoL₂]（1）,[ZnL₂]（2）及[CuL₂]（3）,所得化合物结构通过元素分析、红外光谱、核磁共振谱及X射线单晶衍射法进行表征。生物测试结果表明,配体（L）及配合物1~3对马铃薯干腐病菌、苹果炭疽病菌、苹果腐烂病菌、番茄灰霉病菌4种植物病原菌具有较好的抑菌活性。     

New Hexazirconium Clusters Containing Hydrogen Atoms

Reduction of ZrBr₄ with HSnBu₃ yielded a blue solid. When this blue solid was treated with PMe₃, a hexanuelear cluster [Zr₆Br₁₄H₄( PMe₃)₄] (2) was isolated. Reaction of the blue solid with [PPh₄]Br in CH₂Cl₂ resulted in the formation of a paramagnetic and unstable cluster anion, [Zr₆Br₁₈H₅]^2– (3), which disproportionated to form a new cluster anion, [Zr₆Br₁₈H₅]^3– (4) and some Zr(IV) species. Compounds containing 4 can also be obtained from reaction of the blue solid with Br^– in MeCN. Reduction of ZrCl₄ with HsnBu₃ gave a red–brown solid, and [Zr₆Cl₁₄H₄(AsMe₃)₄] (9) and [Zr₅Cl₁₂H₄(AsMe₃)₅](8) were obtained by reaction of the red–brown solid with AsMe₃. No cluster compounds containing amine ligands were obtained in the reaction of the red–brown solid with amines; only compounds containing the [Zr₆Cl₁₈ H₅]^3– anion and ammonium cations were isolated. Altogether ten products were characterized by single crystal X-ray diffraction and where possible, by ¹H NMR studies.     

Base-promoted rearrangement of cage α-haloketones—II : 12-oxa-3,5,9,10-tetrachlorohexacyclo[5.4.1.02,6.03,10.05,9.08,11]-dodecane-4-one

A synthesis of 12-oxa-3,5,9,10-tetrachlorohexacyclo[5.4.1.0^2,6.0^3,10.0^5,9.0^8,11]dodecane-4-one (6) from 4,4-dimethoxy-2,3,5,6-tetrachloropentacyclo [[5.4.0.0^2,6.0^3,10.0^5,9]undecane-8,11-dione (1) is described. Reaction of 6 with sodium hydroxide in refluxing benzene, toluene, or tetrahydrofuran affords 11-oxa-3,4,5-exo-6-tetrachloropentacyclo [[6.2.1.0^2,7.0^4,10.0^5,9]undecane-endo-3-carboxylic acid (7a, 80·2% yield). The corresponding reaction of 6 with refluxing aqueous sodium hydroxide solution affords 4,12-dioxa-8,11-dichlorohexacyclo-[5.4.1.0^2,6.0^3,10.0^5,9.0^8,11]dodecane-1-carboxylic acid (8a, 66·5% yield). A mechanism which accounts for the formation of 7a and 8a from 6 is presented.     

Mercury(II) complexes of pyrrolidinedithiocarbamate,crystal structure of bis{[μ2-(pyrrolidinedithiocarbamato-S,S ′)(pyrrolidinedithiocarbamato-S,S ′)mercury(II)]}

Mercury(II) complexes of pyrrolidinedithiocarbamate (PDTC) having the general formula [Hg(PDTC)X] (X = Cl^?, SCN^?, and CN^?) and [Hg(PDTC)₂] have been prepared and characterized by elemental analysis, IR, and NMR. The crystal structure of [Hg(PDTC)₂] has also been determined by X-ray crystallography, showing that the complex is a centrosymmetric dimer, [Hg₂(PDTC)₄] (bis[µ²-(pyrrolidinedithiocarbamato-S,S′)(pyrrolidinedithiocarbamato-S,S′)mercury(II)]) (1). The solid-state structure of 1 contains two crystallographically equivalent Hg(II) centers in a distorted tetrahedron.     

Incorporation of manganese complexes into thioarsenates(V), displaying a new structural motif

Two new manganese thioarsenates(V) [Mn(Hen)₂(AsS₄)₂]·2(Hen) (1, en = ethylenediamine) and β-{[Mn(dien)₂][Mn₂(dien)₂(AsS₄)₂] (2, dien = diethyleneamine) have been solvothermally synthesized and structurally characterized. 1 contains [Mn(Hen)₂(AsS₄)₂]^2? built from two [AsS₄]^3? anions bound to [Mn(Hen)₂]⁴⁺, and two protonated Hen⁺ cations, which provide a rare example of monoprotonated ethylenediamine as monodentate ligand within chalcogenidoarsenates. 2 contains two conformations of a [Mn₂(dien)₂(AsS₄)₂]^2? cluster constructed from two [Mn(dien)]²⁺ groups bridged by two μ-[AsS₄]^3? anions and charge compensating complex cations [Mn(dien)₂]²⁺. Their optical properties have been characterized by UV–vis spectra and the theoretical band structure of 1 has also been studied.     

Trimacrocyclic hexasubstituted benzene linked by labile octahedral [X(CHCl3)6]− clusters

Crystalline supramolecular architectures mediated by cations, anions, ion pairs or neutral guest species are well established. However, the robust crystallization of a well-designed receptor mediated by labile anionic solvate clusters remains unexplored. Herein, we describe the synthesis and crystalline behaviors of a trimacrocyclic hexasubstituted benzene 2 in the presence of guanidium halide salts and chloroform. Halide hexasolvate clusters, viz. [Cl(CHCl₃)₆]⁻, [Br(CHCl₃)₆]⁻, and [I(CHCl₃)₆]⁻, were found to be critical to the crystallization process, as suggested by the single-crystal structures, X-ray powder diffraction (XRPD), thermogravimetric analysis (TGA), scanning electron microscopy with energy dispersive spectroscopy (SEM-EDS), and NMR spectroscopy. This study demonstrates the hitherto unexpected role that labile ionic solvate clusters can play in stabilizing supramolecular architectures.

We report the synthesis and robust crystallization of a trimacrocyclic hexasubstituted benzene and guanidium mediated by unprecedented labile halide hexasolvate clusters, viz. [Cl(CHCl₃)₆]⁻, [Br(CHCl₃)₆]⁻, [I(CHCl₃)₆]⁻, and [Br(CHBr₃)₆]⁻.     

(18-Crown-6)potassium tetrachloroferrate(III), dibromodichloroferrate(III), and tetrabromoferrate(III): Synthesis and crystal structures

Three new crystalline complexes are synthesized: [K(18-crown-6)]⁺ · An, where An = [FeCl₄]^?(I), [FeBr₂Cl₂]^? (II), and [FeBr₄]^? (III). The crystals of compounds I–III are cubic and isomorphic, space group Fd $ \bar 3 Three new crystalline complexes are synthesized: [K(18-crown-6)]⁺ · An, where An = [FeCl₄]⁻(I), [FeBr₂Cl₂]⁻ (II), and [FeBr₄]⁻ (III). The crystals of compounds I–III are cubic and isomorphic, space group Fd (Z = 16): a = 20.770(2) ? for I, 20.844(3) ? for II, and 20.878(4) ? for III. Structures I–III are solved by a direct method and refined by the full-matrix least-squares method in the anisotropic approximation to R = 0.047 (I), 0.059 (II), and 0.098 (III) for all 680 (I), 684 (II), and 686 (III) independent reflections. In two tetrahedral anions [Fe(1)X₄]⁻ and [Fe(2)X₄]⁻ in structures I–III, all halogen atoms (X = Cl and Br) are randomly disordered over three close positions relative to the crystallographic axes 3. Structures I–III contain the [K(18-crown-6)]⁺ host-quest complex cation. The K⁺ cation (CN = 8) resides in the cavity of the 18-crown-6 ligand and coordinated by its six O atoms and two disordered halogen X atoms. The coordination polyhedron of the K⁺ cation in complexes I–III is a distorted hexagonal bipyramid. Original Russian Text ? A.N. Chekhlov, 2008, published in Zhurnal Neorganicheskoi Khimii, 2008, Vol. 53, No. 9, pp. 1566–1570.     

Syntheses and characterization of two new compounds based on versatile 1,2,3,5-benzenetetracarboxylic acid and 2,2′-bibenzimidazole

Two coordination complexes based on H₄btec and H₂bibzim (H₄btec = 1,2,3,5-benzenetetracarboxylic acid, H₂bibzim = 2,2′-bibenzimidazole), [Ni(H₂bibzim)₃]₂(btec) (1) and [Zn(H₂bibzim)(btec)_0.5]_n (2), have been synthesized by hydrothermal methods and characterized by single-crystal X-ray diffraction. Complex 1 is composed of [Ni(H₂bibzim)₃]²⁺ with free btec^4? as counter anion. In 2, the btec^4? ligands bridge the Zn(II) ions into a 1-D chain with H₂bibzim as auxiliary chelating ligands. Interesting supramolecular structures were demonstrated due to the existence of hydrogen bonding as well as π?π interactions in the two different complexes. The H₂bibzim ligands act as a 2-connected spacer in both complexes. However, in 1, the [Ni(H₂bibzim)₃]²⁺ cations act as 3-connected nodes, hydrogen bonded with the 6-connected btec^4? ligands into a 3-D framework with (3,6)-connected topology Schläfli symbol as (4.6.8)(4².6)(4³.6⁴.8⁷.10). As for 2, Zn serves as a 3-connected node with btec^4? as a 6-connected node, leading to a 2D (3,6)-connected hydrogen bonding kgd topology sheet with Schläfli symbol of (4³)²(4⁶.6⁶.8³). Thermal stabilities and photoluminescent properties of 1 and 2 were also studied.     

Synthesis and structural characterization of ruthenium complexes with 1-aryl-imidazole-2-thione

Treatment of [RuCl₂(PPh₃)₃] with 2 equiv. Himt^MPh (Himt^MPh?=?1-(4-methyl-phenyl)-imidazole-2-thione) in the presence of MeONa afforded cis-[Ru(κ ²-S,N-imt^MPh)₂(PPh₃)₂] (1), while interaction of [RuCl₂(PPh₃)₃] and 2 equiv. Himt^MPh in tetrahydrofuran (THF) without base gave [RuCl₂(κ ¹-S-Himt^MPh)₂(PPh₃)₂] (2). Treatment of [RuHCl(CO)(PPh₃)₃] with 1 equiv. Himt^MPh in THF gave [RuHCl(κ ¹-S-Himt^MPh)(CO)(PPh₃)₂] (3), whereas reaction of [RuHCl(CO)(PPh₃)₃] with 1 equiv. of the deprotonated [imt^MPh]^? or [imt^NPh]^? (imt^NPh?=?1-(4-nitro-phenyl)-2-mercaptoimidazolyl) gave [RuH(κ ²-S,N-imt^RPh)(CO)(PPh₃)₂] (R?=?M 4a, R?=?N 4b). The ruthenium hydride complexes 4a and 4b easily convert to their corresponding ruthenium chloride complexes [RuCl(κ ²-S,N-imt^MPh)(CO)(PPh₃)₂] (5a) and [RuCl(κ ²-S,N-imt^NPh)(CO)(PPh₃)₂] (5b), respectively, in refluxing CHCl₃ by chloride substitution of the RuH. Photolysis of 5a in CHCl₃ at room temperature afforded an oxidized product [RuCl₂(κ ²-S,N-imt^MPh)(PPh₃)₂] (6). Reaction of 6 with excess [imt^MPh]^? afforded 1. The molecular structures of 1·EtOH, 3·C₆H₁₄, 4b·0.25CH₃COCH₃, and 6·2CH₂Cl₂ have been determined by single-crystal X-ray crystallography.     

Synthesis and Characterization of Diastereoisomerically Pure Tetracyclo[6.2.1.13,6.02,7]dodec‐9‐ene‐4‐carboxylic Acid Derivatives

The synthesis and detailed NMR analysis of diastereoisomerically pure samples of 4‐methyltetracyclo[6.2.1.1^3,6.0^2,7]dodec‐9‐ene‐4‐carboxylic acid ( 2 ), tetracyclo[6.2.1.1^3,6.0^2,7]dodec‐9‐ene‐4‐carboxylic acid ( 6 ) and their tert‐butyl esters are reported. Mixtures containing two isomers of the methyl esters of these compounds were obtained by a twofold, sequential Diels‐Alder reaction between cyclopentadiene, and methyl methacrylate or methyl acrylate, respectively. Pure diastereoisomers of the acids were prepared by selective hydrolysis of their methyl esters.     

Synthesis,structures, and spectroscopic properties of Hg(II) complexes of bidentate NN and tridentate NNO Schiff-base ligands

Reactions of HgX₂ (X?=?Cl, N₃, NO₃) with (E)-2-methoxy-N-(pyridin-2-ylmethylene)aniline (L¹) and (E)-4-methoxy-N-(pyridin-2-ylmethylene)aniline (L²) in ethanol gave two monomers, [HgL¹(Cl)₂] (1) and [HgL²(NO₃)₂(DMSO)] (5), and three coordination polymers, {[HgL¹(N₃)₂]₂·Hg(N₃)₂}_n (2), [HgL²(Cl)₂]_n (3), and [HgL²(NO₃)₂]_n·nCH₃CN (4). Compounds 1–5 were characterized by elemental analysis, IR, NMR spectroscopy, and single-crystal X-ray diffraction. The common feature of monomeric 1 and 5 is the presence of intra- and intermolecular Hg–O bonds. In the absence of these, polymeric structures arise as a result of azide, chloride, and nitrate bridging in 2, 3, and 4, respectively. Fluorescent properties of 1–5 were also investigated.     

Cobalt(II) complexes with pyridine and 5-[(E)-2-(aryl)-1-diazenyl]-quinolin-8-olates: synthesis,electrochemistry and X-ray structural characterization

Abstract

Nine new cobalt(II) compounds, trans-[Co(L^PAQ)₂(Py)₂] (1), trans-[Co(L^PAQ)₂(3-MePy)₂] (2), trans-[Co(L^MeAQ)₂(Py)₂] (3), trans-[Co(L^OMeAQ)₂(Py)₂] (4), trans-[Co(L^OEtAQ)₂(Py)₂]·2(H₂O) (5), trans-[Co(L^CAQ)₂(Py)₂] (6), trans-[Co(L^BAQ)₂(Py)₂] (7), cis-[Co(L^BAQ)₂(3-MePy)₂] (8a) and trans-[Co(L^BAQ)₂(3-MePy)₂]·2(3-MePy) (8b) (primary ligand: L^XAQ?=?substituted 5-[(E)-2-(aryl)-1-diazenyl]quinolin-8-olate; secondary ligands: Py?=?pyridine, 3-MePy = 3-methylpyridine), have been synthesized and characterized by elemental analysis, IR and UV-vis spectroscopy. Magnetic measurements of the cobalt compounds were performed in solution by ¹H NMR spectroscopy using the Evans’ method while their redox properties were studied by cyclic voltammetry. Single-crystal X-ray diffraction analysis of the compounds revealed their octahedral geometries and trans configuration, except for 8a, which has a cis configuration. Intermolecular noncovalent interactions were detected, π···π interactions in 5, C?–?H···π interactions in 2 and C?–?H···π edge-to-face (T-shaped) arrangements in 3, 4, 6, and 7.     

Synthesis of Polyfunctionally Substituted Pyrazolonaphthyridine,Pentaazanaphthalene, and Heptaazaphenanthrene Derivatives

6-aminopyrazolo[3,4-b]pyridine-5-carbonitrile (2) was used as a precursor for the synthesis of a variety of pyrazolo[3,4-b][1,8]naphthyridines (3, 4) and pentaazacyclopenta[b]naphthalenes (5–10, 13, 14) via the initial addition to either the cyano or amino group followed by cyclization. Also, a series of heptaazadicyclopenta[a,g]naphthalenes (15–17) and heptaazacyclopenta[b]phenanthrenes (18, 19) were obtained via the interaction of 4-(dibenzothiophen-2-yl)-1,5-dihydro-5-imino-3-methyl-1-phenyl-1,2,6,8,9-pentaazacyclopenta[b]naphthalen-6-ylamine (14) with different reagents. The structures of the synthesized compounds were established by elemental and spectral analyses.     

Studies on mononuclear transition metal chelates derived from a novel ( E,E )-dioxime: synthesis,characterization and biological activity

A novel vic-dioxime ligand with a thiourea moiety, (4E,5E)-1,3-bis{4-[(4-bromophenylamino)methylene]phenyl}-2-thiooxaimidazoline-4,5-dione dioxime (4) (bmdH₂) has been synthesized from N,N′-bis{4-[(4-bromophenylamino)methylene]phenyl}thiourea and (E,E)-dichloroglyoxime. The bmdH₂ ligand (4) forms transition metal complexes [M(bmdH)₂] with a metal?:?ligand ratio of 1?:?2 with M?=?Ni(II), Co(II), and Cu(II). The mononuclear Ni(II), Co(II) and Cu(II) complexes, [Ni(bmdH)₂] (5), [Co(bmdH)₂] (6) and [Cu(bmdH)₂] (7) have the metal ions coordinated through the two N,N atoms, as do most vic-dioximes. Elemental analyses, molar conductivity, magnetic susceptibility, IR, ¹H NMR spectra, and UV-Visible spectroscopy were used to elucidate the structures of the ligand and its complexes. Conductivity measurements have shown that the mononuclear complexes are non-electrolytes. In addition, the ligands and metal complexes were screened for antibacterial and antifungal activities by agar well diffusion techniques using DMF as solvent.