Volume 67, Issue 9

A new decavanadate [Zn(en) 2 ] 3 [V 10 O 28 ] 5H 2 O (1), (en=ethylenediamine) has been hydrothermally synthesized and characterized by elemental analysis, infrared spectroscopy, thermogravimetry, and single-crystal X-ray diffraction. It is a structural feature of compound 1 that each [V 10 O 28 ] 6- cluster provides four bridging oxygen atoms of two pairs of opposite [VO 6 ] octahedra to graft four [Zn(en) 2 ] 2+ complexes, observed for the first time for the [V 10 O 28 ] 6- cluster. The resulting array represents the second example of a chain based on these decavanadates linked by transition metal complexes Graphical Abstract An Unusual Chain Structure of Decavanadates V 10 O 28 Linked by Zn(en) 2 Units

A new 1D polyoxovanadate containing boric acid [Cu(en) 2 V 10 O 28 ][Cu(en) 2 (H 2 O)] 2 2H 3 BO 3 2H 2 O (1, en=ethylenediamine) has been hydrothermally synthesized and structurally characterized. Compound 1 consists of a polyoxovanadate chain [Cu(en)2V 10 O 4- 28 ]n based on the linkage of decavanadate clusters and [Cu(en) 2 ] 2+ groups, complex cations [Cu(en) 2 (H 2 O)] 2+ , free H 3 BO 3 and H 2 O molecules. The polyoxovanadates and boric acid can undergo polycondensation into various B-O-V clusters under hydrothermal conditions, but 1 is the only example of the non-condensation of polyoxovanadate and boric acid. The IR spectrum and the thermal behavior of 1 were also studied Graphical Abstract A New 1D Polyoxovanadate [Cu(en) 2 V 10 O 28 ][Cu(en) 2 (H 2 O)] 2 2H 3 BO 3 2H 2 O Containing the Rarely Non-condensed Boric acid

Two cyclometalated iridium(III) complexes, Ir(dpppz)(ppz)(ipx) and Ir(ppz) 2 (ipx) (dpppzH=1- (2,6-dimethylphenoxy)-4-phenylphthalazine, ppzH=4-phenylphthalazinone, ipx=isopropyl xanthate), have been synthesized and characterized by single-crystal X-ray diffraction. The photophysical properties of the two complexes were also investigated. Ir(dpppz)(ppz)(ipx) shows orange-red emission at around 606 nm with a phosphorescence quantum yield of ca. 0.0032 and an emission lifetime of 188 ns, while Ir(ppz) 2 (ipx) shows orange-red emission at around 599 nm with a phosphorescence quantum yield of ca. 0.00318 and an emission lifetime of 259 ns. The phosphorescence behavior of Ir(ppz) 2 (ipx) towards different metal cations has also be studied. Its strong phosphorescence is quenched by Hg 2+ , Cu 2+ and Ag + cations. The interaction ratio with Hg 2+ is 1:1 Graphical Abstract Novel Cyclometalated Iridium(III) Xanthate Complexes and Their Phosphorescence Behavior in the Presence of Metal Ions

A new complex Cu 2 (phen) 2 [C 7 H 8 (COO) 2 ] 2 (H 2 O) 4:5 (1) has been synthesized, with the dianion of bicyclo[2.2.1] hept-2-ene-5,6-dicarboxylic acid [C 7 H 8 (COOH) 2 ] (LH 2 ) and 1,10-phenanthroline (phen) as ligands. In 1, L 2- anions link Cu(II) cations to form two binuclear structure units, in which each Cu(II) cation is coordinated by five donor atoms to give a distorted square-pyramidal geometry. The magnetic data of 1 show that it exhibits weak antiferromagnetic properties at low temperature. When the excitation wavelength is at 470 nm, it has an intense photoluminescence. In addition, the cyclovoltammetric electron transfer is quasi reversible in the electrode reaction of 1, two electrons being involved in the reaction corresponding to Cu(II)=Cu(0) Graphical Abstract Crystal Structure and Properties of a New Copper(II) Complex Cu 2 (phen) 2 [C 7 H 8 (COO) 2 ] 2 (H 2 O) 4:5

Two new two-dimensional copper(II) coordination polymers, [Cu(L)(BDC)]_H2O (1) and [Cu 2 (L) 0:5 (SIP)(OH)(H 2 O)] 2H 2 O (2) [L=N;N0-bis(3-pyridylamide)-1,6-hexane, H 2 BDC=1,3- benzenedicarboxylic acid, H 3 SIP=5-sulfoisophthalic acid (3,5-dicarboxybenzenesulfonic acid)], have been synthesized hydrothermally by self-assembly of the flexible bis-pyridyl-bis-amide ligand L and the aromatic polycarboxylate ligands H 2 BDC or H 3 SIP. X-Ray diffraction analysis reveals that complex 1 displays a metal-organic coordination layer with a binodal (3,5)-connected {42.67.8}{42.6} topology, in which the L ligands adopt a m2-bridging mode (via ligation of the pyridyl nitrogen atoms). Complex 2 also exhibits a layered network based on tetranuclear copper clusters [Cu 4 (μ 3 -OH) 2 (H 2 O) 2 (O 2 C-) 4 ], L ligands and SIP anions, showing a binodal (4,8)-connected network with {4 14 .6 10 .8 4 }{4 4 .6 2 } topology, in which the L ligands adopt a μ 6 -bridging coordination mode (via ligation of the pyridyl nitrogen and carbonyl oxygen atoms). Adjacent layers in 1 and 2 are further linked by hydrogen bonding interactions to form three-dimensional supramolecular frameworks. The electrochemical behavior of the two complexes in bulk-modified carbon paste electrodes has been investigated Graphical Abstract The Role of the Coordination Modes of a Flexible Bis(pyridylamide) Ligand in the Topology of 2D Copper(II) Complexes

Lithiation of 1,2-dichloro- or 1,2,3-trichloroferrocene with lithium tetramethylpiperidinide, followed by transmetallation with ZnCl 2 and Pd(II)-catalyzed coupling with 2-bromopyridine, yield the pyridylferrocenes [CpFe{C 5 H 2-n Cl 2+n (2-C 5 H 4 N)}] (2a, b, n=0 or 1) as brown oils of low stability. Recrystallization of 2b produced a small number of X-ray quality crystals, which could be shown to have the proposed constitution. However, from the recrystallization solution of 2a a few crystals precipitated whose X-ray structure determination identified them as a metal-free phosphonium ylide {C 5 HCl 2 (2-C 5 H 4 N)(PPh 3 )} (3) Graphical Abstract Komplexchemie perhalogenierter Cyclopentadiene und Alkine, Teil 31 [1]. Darstellung von 2,3-Dichlor- und 2,3,4-Trichlor-1-(2-pyridyl)ferrocen [CpFe{C5H2-nCl2+n(2-C 5 H 4 N)}] (n=0, 1). Molekülstrukturen von [Cpe{C 5 HCl 3 (2-C 5 H 4 N)}] und {C 5 HCl 2 (PPh 3 )(2-C 5 H 4 N)g, einem unerwarteten Nebenprodukt / Coordination Chemistry of Perhalogenated Cyclopentadienes and Alkynes, Part 31. Synthesis of 2,3-Dichloro- and 2,3,4-Trichloro-1-(2-pyridyl)ferrocene [CpFe{C 5 H 2-n Cl 2+n (2-C 5 H 4 N)}] (n=0, 1). Molecular Structures of [CpFe{C 5 HCl 3 (2-C 5 H 4 N)}] and {C 5 HCl 2 (PPh 3 )(2-C 5 H 4 N)}, an Unexpected Side Product

Ba 20 Hg 103 , the next Hg-rich binary barium mercuride after BaHg 11 and BaHg 6 , was synthesized from melts of the elements, which were slowly cooled from 550 to 200 °C. It forms a new complex cubic structure type (F43m, a = 2333.30(10) pm, Z = 4, R1 = 0.0651) with four Ba und 13 Hg positions as determined by means of single-crystal X-ray diffraction. The structure can be best described by decomposing it into four types (A to D) of space-filling distorted truncated octahedra (sodalite or b-cages) centered at the four sites with 43m point group symmetry of the space group. The cages C and D are centered by [Hg 8 ] tetrahedra stars, which are connected via [Hg(13)Hg 8 ] cubes to form a diamond-type network. The polyhedra B contain a section of the Laves phaseMgCu 2 (five [Hg 4 ] tetrahedra sharing corners). The smallest polyhedron A contains a truncated tetrahedron [HgHg 12 ] surrounded by a strongly covalently bonded mercury shell. The ternary cadmium derivative Ba 20 Cd 4 Hg 99 (a = 2331.57(14) pm, R1 = 0.0465) is isotypic, whereas in the related zinc mercuride Ba 20 Zn 5 Hg 99 (a = 2332.33(7) pm, R1 = 0.0436) one of the tetrahedra stars is filled by an extra zinc atom and is thus distorted into a [ZnHg 8 ] cube. This extra zinc atom causes the small change in the compounds formula. The four crystallographically different Ba cations are coordinated by 17 or 18 Hg atoms. The mercury atoms themselves are surrounded by 10 to 13, in one case 16, Hg=Ba neighbors. The shortest Hg-Hg distances (d min Hg-Hg = 285:8 pm) are found for the strong covalent bonds in the shell around the sodalite cages A and the cubes around Hg(13). The bonding modes (Hg-Hg distances and overall coordinations numbers) of the different Hg atoms of Ba 20 Hg 103 are discussed in comparison with those in the more Hg-rich compounds BaHg 6 and BaHg 11 . According to their crystal-chemical properties, the Hg atoms in Hg-rich mercurides can be classified into four different groups, from mainly covalent to polar intermetallic and pure metallic, to finally cationic centers Graphical Abstract Das neue komplexe Barium-Mercurid Ba 20 Hg 103 und seine ternären Zink- und Cadmium-Varianten / The New Complex Barium Mercuride Ba 20 Hg 103 and its Ternary Zinc and Cadmium Variants

1,3-Dimethyl-5-imino-imidazolidine-2,4-dione (7a) undergoes thiolysis (H 2 S) to give the corresponding imidazolidine-2,4-dione-5-thione derivative 6. The 5-N-methylimino analogue 7b can be obtained from 7a by methylation. Further methylation of 7b affords the crude iminium salt 8c from which the heterocyclic orthoamide derivatives 10, 11 can be prepared. The heterocyclic amide acetal 9a can be obtained from 7a and dimethyl sulfate in methanol and subsequent addition of sodium methanolate in a one-pot reaction. The aminal ester 10 is converted to the amide acetal 9a on treatment with hydrogen chloride in methanol Graphical Abstract Orthoamide und Iminiumsalze, LXXXI [1]. Orthoamid-Derivate der 1,3-Dimethylparabansäure / Orthoamides and Iminium Salts LXXXI [1]. Orthoamide Derivatives of 1,3-Dimethylparabanic Acid

The cleavage of orthoamides of alkynecarboxylic acids 5 with trimethylsilyl azide affords 4-[bis(dimethylamino)methylene]-4H-1,2,3-triazoles 9. By treatment of the bis-orthoamide of acetylenedicarboxylic acid 1 with trimethylsilyl azide and benzoyl azide, respectively, the 5- [bis(dimethylamino)methylene]-5H-1,2,3-triazole carboxamidinium salt 12a is accessible. Iminium salts 10 and 14 can be prepared by methylation of the triazoles 9 and 12a in 2-position of the triazole ring. The crystal structure of 5H-1,2,3-triazole-4-carboxamidinium tetraphenylborate 12b is reported Graphical Abstract Orthoamide und Iminiumsalze, LXXXII [1]. Die Spaltung von Alkincarbonsäure-orthoamiden mit Trimethylsilylazid / Orthoamides and Iminium Salts LXXXII [1]. The Cleavage of Orthoamides of Alkynecarboxylic Acids by Trimethylsilyl Azide

4-Chloroalkyl-3,4-dihydropyrimidin-2(1H)-ones are useful multifunctional 3,4-dihydropyrimidine building blocks with low molecular weight and sufficient solubility, which may be modified selectively by substituents in different positions. Here we propose a simple one-pot protocol for the synthesis of these compounds, which is based on the use of common reagents viz. urea, chloroaliphatic aldehydes and 3-ketoesters. Acylation of 4-chloroalkyl-3,4-dihydropyrimidin-2(1H)-ones by carboxylic acid anhydrides leads to 3-acyl derivatives Graphical Abstract Synthesis and Acylation of 4-Chloroalkyl-3,4-dihydropyrimidin-2(1H)- ones

The development of new HIV non-nucleoside reverse transcriptase inhibitors (NNRTIs) offers the possibility of generating structures of increased potency. To this end, a series of 1-(1-benzyl-2-ethyl- 4-nitro-1H-imidazol-5-yl)-4-(1,1'-biaryl)-4-yl-piperazine derivatives (6a-l) was synthesized via the Suzuki coupling reaction. Analogously, coupling of the acid derivative 5, prepared from 4, with various amino acid methyl esters in the presence of HOBt/DCC reagents afforded the benzamide derivatives 8-11. The newly synthesized compounds were assayed against HIV-1 and HIV-2 in MT- 4 cells. All compounds are inactive, except compound 6f which showed inhibition of HIV-1 with EC 50 = 2:60μgmL -1 with a selectivity index (SI) of 9 Graphical Abstract Nitroimidazoles Part 8. Synthesis and Anti-HIV Activity of New 4-Nitroimidazole Derivatives Using the Suzuki Cross-Coupling Reaction

With Heitler-London atomic orbital-type formulations of the wave functions for (fractional) electron-pair π x (NN) and π y (NN) bonds, increased-valence structures for the N 3 - anion and N 3 - radical are equivalent to resonance between familiar standard Lewis structures and singlet diradical (or “long-bond”) Lewis structures. Theory is developed for the calculation of the polarity parameters that are associated with the one-electron π x (NN) and π y (NN) bonds in the increased-valence structures, and illustrative STO-6G estimates of their values are reported. They show that the π x and π y electrons of these bonds are strongly charge-correlated relative to each other. The increased-valence structures for the N 3 - anion and the N 3 - radical are used to help construct increased-valence structures for the N 6 - radical anion with C 2h symmetry Graphical Abstract Valence Bond Structures for the N 3 - Anion, the N 3 Radical and the N 6 - Radical Anion

Two new haliclamines were identified directly from the crude extract of the Arctic sponge Haliclona viscosa using improved chromatographic conditions and a detailed knowledge about the fragmentation pattern of haliclamines. These are haliclamine G (1) with two alkyl chains of equal length (10 methylene groups) and haliclamine H (2) with alkyl chains of 10 and 12 methylene groups. Due to the limited amount of sponge material available, the haliclamines were not isolated, and the structure elucidation relied on the chromatographic and mass spectrometric comparison with synthetic compounds Graphical Abstract Structure Elucidation of Submilligram Quantities of Natural Products - Application to Haliclamines G and H from the Arctic Marine Sponge Haliclona viscosa

A metal-organic framework [Cd(dppip)]n (1) based on 5-(diphenylphosphino)isophthalic acid (H 2 dppip) has been synthesized hydrothermally and characterized by IR spectroscopy, elemental analysis, and X-ray crystallography. [Cd(dppip)] n shows a sheet structure owing to carboxylate bridging with windows with dimensions 10.692 x 9.325 Å 2 . The layers are further connected through P-Cd interactions to give a three-dimensional supramolecular network. The thermal analysis (DTA) of complex 1 exhibited an exceptionally high thermal stability (m. p. 452:8 °C). The compound shows fluorescence at ca. 418 nm upon excitation at 314 nm Graphical Abstract Hydrothermal Synthesis, Crystal Structure and Properties of a Novel Phosphorus-containing 3D Metal- Organic Cd(II) Coordination Polymer