Volume 64, Issue 2

In the presence of [NBu 4 ][PF 6 ] as the electrolyte, thianthrene (TA) is transformed by electrochemical oxidation to thianthrenium hexafluorophosphate containing the TA •+ radical cation. The reactions were performed in CH 2 Cl 2 , H 3 CCN, and liquid SO 2 as solvents. In CH 2 Cl 2 , TA[PF 6 ] is sparingly soluble and is deposited directly in crystalline form on the platinum electrode. In H 3 CCN and liquid SO 2 , TA[PF 6 ] is highly soluble and gives dark blue solutions from which it can be crystallized upon concentration of the solutions. The air sensitive crystals are black with bronze metallic luster. They belong to the monoclinic system (C2/m, a = 12.4345(8), b = 10.5318(6), c = 11.1303(7) Å , β = 112.565(3)◦) and are built up of almost planar TA •+ cations and octahedral [PF 6 ]− anions. The F atoms of the anions are disordered over two positions. The radical cations are associated to form dimeric units (TA •+ )2 with the planar molecules stacked with two weak S· · ·S bonds (3.06 Å ). In the crystal these dimers are separated by the [PF 6 ]− anions. Electrical conductivity measurements show TA[PF 6 ] to be a small-gap semiconductor. Conductivity is low at r. t. but reaches 2.5 · 10 −5 S m −1 at 110 °C, the activation energy in the high-temperature region amounts to 1.2 eV. Periodic quantum-chemical calculations at hybrid density-functional level predict a strong coupling between neighboring (TA •+ ) spin centers, resulting in a singlet ground state. The calculated band gaps of both singlet (1.5 eV) and triplet (0.9 eV) states are small, consistent with the measured conductivity Graphical Abstract Thianthrene Radical Cation Hexafluorophosphate

The reactions of N 1 ,N 2 -Di-boc-1,2,4-triaminobutane with bridged dicarboxylic acids afford the corresponding bis-amides from which - after removal of the Boc groups - bis(N,N'-bidendate) ligands H 2 NCH 2 CH(NH 2 )(CH 2 ) 2 NHCO-X-CONH(CH 2 )2CH(NH 2 )CH 2 NH 2 can be obtained. New examples are the reactions of the triaminobutane with pyridine-2,6-dicarboxylic acid, with phenylene- 1,4-diacetic acid, with terephthalic acid dichloride and with benzene-1,2,4,5-tetracarboxylic acid. From the new ligands with two terminal ethylenediamine groups, the bis(dichloroplatinum) complexes were synthesized Graphical Abstract Hydrocarbon-bridged Metal Complexes, LII [1]. N 1 ,N 2 -Di(tert-butoxycarbonyl)-1,2,4-triaminobutane, a Useful Reagent for the Synthesis of Hydrocarbon-bridged Bis(ethylenediamine) Ligands by Reactions with Dicarboxylic Acids

3,4-Bisarylpyrrole-2,5-dicarboxylic acids were coupled with rac-N 1 ,N 2 -di-Boc-1,2,4-triaminobutane to give the corresponding diamides, which were deprotected and converted into the bis(cis-dichloroplatinum) complexes by treatment with K 2 PtCl 4 Graphical Abstract Metal Complexes of Biologically Important Ligands, CLXXI [1]. Incorporation of the cis-Dichloroplatinum Group into Amides of 3,4-Diarylpyrrole-2,5-dicarboxylic Acids

The coupling of the tricarboxylic acids, 1,3,5-benzene-tricarboxylic acid, cis,cis-1,3,5-cyclohexane- tricarboxylic acid and of citric acid, with rac-N 1 ,N 2 -di-Boc-1,2,4-triaminobutane affords the corresponding triamides which were deprotected. From the novel tris(bidendate) ligands with three terminal ethylenediamine donors the tris(cis-dichloro platinum) complexes were obtained Graphical Abstract Hydrocarbon-bridged Metal Complexes, LIII [1]. Trinuclear (cis-Dichloro-ethylenediamine) Platinum(II) Complexes from Amides of Tricarboxylic Acids and 1,2,4-Triaminobutane

The platinum-rich intermetallic compounds GdPt 2 In and GdPt 2 Sn were synthesized by arc-melting of the elements and subsequent annealing. The structures were refined from single crystal X-ray diffractometer data: ZrPt 2 Al type, space group P6 3 /mmc, a = 455.1(1), c = 899.3(3) pm, wR2 = 0.0361, 166 F 2 values, 9 variables for GdPt 2 In, and a = 453.2(1), c = 906.5(2) pm, wR2 = 0.0915, 166 F 2 values, 9 variables for GdPt 2 Sn. The platinum and indium (tin) atoms build up threedimensional [Pt 2 In] and [Pt 2 Sn] networks with short Pt-In (Pt-Sn) distances and Pt 2 dumb-bells (290 and 297 pm in GdPt 2 In and GdPt 2 Sn). The gadolinium atoms have coordination number 14 with 8 Pt and 6 In (Sn) neighbors. Magnetic susceptibility measurements on GdPt 2 In show Curie-Weiss behavior with an experimental magnetic moment of 8.06(2) μB/Gd atom. GdPt 2 In orders ferromagnetically at 27.7(2) K Graphical Abstract Structure and Magnetic Properties of GdPt 2 In and GdPt 2 Sn

The stannide CeZnSn was obtained in X-ray-pure form by induction-melting of the elements in a sealed tantalum ampoule. CeZnSn crystallizes with the YPtAs-type structure, space group P6 3 /mmc, a = 456.7(3), c = 1673.8(5) pm, wR2 = 0.0862, 259 F 2 values, and 12 variables. The zinc and tin atoms build up puckered Zn3Sn3 hexagons (Zn-Sn 271 pm) with weak interlayer Zn-Zn interactions (323 pm). Susceptibility measurements of CeZnSn reveal modified Curie-Weiss behavior above 50 K with an experimental magnetic moment of 2.77(1) μ B / Ce atom. The cerium magnetic moments order ferromagnetically at T C = 5.2(1) K. 119 Sn Mössbauer spectra show a single tin site at an isomer shift of δ = 1.967(4) mm/s subjected to a small quadrupole splitting of ΔE Q = 0.41(2) mm/s at 40 K. At 4.2 K a magnetic hyperfine field of 0.872(5) T is transferred to the tin site. From DFT scalar relativistic calculations of the electronic and magnetic structures, chemical bonding analysis reveals on one hand a weaker bonding of Zn than of Sn with the cerium substructures with a twice stronger Ce1-Sn bond compared to Ce2-Sn. On the other hand, a ferromagnetic ground state is identified from total energy differences in agreement with experiment Graphical Abstract Ferromagnetic Ordering in CeZnSn

The rare earth-rich intermetallic compounds RE 23 T 7 CD 4 (RE = La-Nd, Sm, Gd, Tb; T = Co, Ni, Ru, Rh, Ir, Pt) were synthesized by melting of the elements in sealed tantalum tubes in a high frequency furnace. They crystallize with the Pr 23 Ir 7 Mg 4 -type structure, space group P6 3 mc, Z = 2. The structures of La 23 Pt 7 Cd 4 (a = 1025.4(2), c = 2319.5(5) pm, wR2 = 0.0425, 2587 F 2 , 74 variables), La 23 Ru 6.87(1) Cd 4 (a = 1015.0(2), c = 2282.8(4) pm, wR2 = 0.0383, 2459 F 2 , 75 variables), and Nd 23 Rh 7 Cd 4 (a = 990.0(2), c = 2239.0(5) pm, wR2 = 0.0507, 2350 F 2 , 74 variables) were refined from single crystal X-ray diffractometer data. Central structural motifs of the RE 23 T 7 Cd 4 compounds are transition metal-centered trigonal prisms of rare earth atoms and Cd 4 tetrahedra. The RE 6 T prisms are condensed via common edges and corners, leading to three-dimensional networks. Typical interatomic distances in the prismatic network and in the Cd 4 tetrahedra are 295 - 313 pm La-Pt and 319 - 325 pm Cd-Cd, respectively (examplarily for La 23 Pt 7 Cd 4 ) Graphical Abstract Rare Earth-rich Cadmium Compounds RE 23 T 7 Cd 4 (T = Co, Ni, Ru, Rh, Ir, Pt)

α-CeS 2 and α-NdS 2 were obtained by a metathesis reaction of the anhydrous trichlorides LnCl 3 (Ln = Ce, Nd) and Na 2 S 2 at 1070 K. The two compounds adopt a monoclinic structure type, the so-called CeSe 2 or α-type of the rare earth metal dichalcogenides (space group P2 1 /a), with lattice parameters of a = 8.105(3), b = 4.075(1), c = 8.097(3) Å, β = 90.03(4)◦ for CeS 2 and a = 8.008(2), b = 4.019(1), c = 8.032(2) Å , β = 90.00(3)◦ for NdS 2 . Single crystals of β -LaS 2 , β -CeS 2 and β -PrS 2 were obtained as by-products in the syntheses of the ternary copper sulfides CuLnS2 by reacting the elemental educts (Cu, S and Ln = La, Ce, Pr) in a CsCl flux at 970 K. These compounds adopt the orthorhombic β -LaS 2 structure type (space group Pnma) with lattice parameters of a = 8.140(1), b = 16.379(1), c = 4.144(1) Å for β -LaS2, a = 8.068(1), b = 16.216(1), c = 4.095(1) Å for β -CeS 2 , and a = 8.044(1), b = 16.160(1), c = 4.073(1) Å for β -PrS2 Graphical Abstract Lanthanoiddisulfide – Synthesen und Kristallstrukturen von α-CeS 2 , α-NdS 2 , β-LaS 2 , β-CeS 2 und β-PrS 2 / Rare Earth Metal Disulfides – Syntheses and Crystal Structures of α-CeS 2 , α-NdS 2 , β -LaS 2 , β -CeS 2 , and β -PrS 2

Pale violet, plate-like single crystals of the title compound, neodymium(III) oxide chloride oxotellurate( IV) Nd 5 O 4 Cl 3 [TeO 3 ] 2 , can be obtained by the reaction of Nd 2 O 3 with NdCl 3 and TeO 2 in equimolar ratios in evacuated silica ampoules within five days at 775 °C with an excess of CsCl added as fluxing agent. Nd 5 O 4 Cl 3 [TeO 3 ] 2 crystallizes in the monoclinic space group C 2 /m (no. 12) with the lattice parameters a = 1270.61(9), b = 562.70(4), c = 1008.97(8) pm, β = 90.784(3)°and Z = 2, and is thus isostructural to the lanthanoid(III) oxide halide oxoselenates(IV) Tb 5 O 4 Cl 3 [SeO 3 ] 2 and Gd 5 O 4 Br 3 [SeO 3 ] 2 . The crystal structure exhibits three crystallographically different Nd 3+ cations, of which (Nd1) 3+ has a purely oxidic coordination sphere of eight oxide anions building up a square prism. (Nd2) 3+ and (Nd3) 3+ are both coordinated by oxide and chloride anions. The coordination polyhedron around (Nd2) 3+ is a trigonal prism of oxide anions that is capped by one chloride anion to give a coordination number of seven. (Nd3) 3+ resides in an eightfold coordination of five oxide and three chloride anions forming a square antiprism. All (O1) 2 − anions are surrounded tetrahedrally by Nd 3+ cations as [ONd 4 ] 10+ units. These tetrahedra share common edges and vertices to generate two-dimensional infinite layers of the composition ∞ 2 { [O 4 Nd 5 ] 7+ } , which extend parallel to the (001) plane. The chloride anions (Cl1) − are connecting those slabs via Nd3-Cl1-Nd3 bridges along the [001] direction, while the (Cl2) − anions alternate with the Te 4+ cations above and below the layers. The three-dimensional crystal structure of Nd 5 O 4 Cl 3 [TeO 3 ] 2 is completed by Te 4+ cations, which are bonded to one (O2) 2 − and two (O3) 2 − anions to form ψ 1 -tetrahedra [TeO 3 ] 2 − with a non binding, stereochemically active electron pair (“lone pair”) pointing into the free space between the chloride-decorated ∞ 2 { [O 4 Nd 5 ] 7+ } layers Graphical Abstract Ein neues Selten-Erd-Metall(III)-Oxidchlorid-Oxotellurat(IV): Nd 5 O 4 Cl 3 [TeO 3 ] 2 / A New Rare Earth-Metal(III) Oxide Chloride Oxotellurate(IV): Nd 5 O 4 Cl 3 [TeO 3 ] 2

Treatment of Ag(CF 3 CO 2 ) with an equivalent of bis(diphenylphosphino)amide (dppa) gave a trinuclear trigonal-bipyramidal silver(I) complex [Ag 3 (μ 3 -Cl) 2 (μ-dppa) 3 ][CF 3 CO 2 ]・CH 2 Cl 2 ・H 2 O ([1] [CF 3 CO 2 ]・CH 2 Cl 2 ・H 2 O). Reaction of AgNO 3 with an equivalent of dppa in the presence of [NH 4 ] [GaCl 4 ] and [Et 4 N][FeCl 4 ] afforded the corresponding complexes [Ag 3 (μ 3 -Cl) 2 (μ-dppa) 3 ][GaCl 4 ]・ 2THF・MeOH・H 2 O, ([1][GaCl 4 ]・2THF・MeOH・H 2 O) and [Ag 3 (μ-Cl)(μ 3 -Cl)(μ-dppa) 3 ][FeCl 4 ], ([2] [FeCl 4 ]), respectively. Complexes 1 and 2 contain trigonal-bipyramidal [Ag 3 (μ 3 -Cl) 2 ] + and [Ag 3 (μ- Cl)(μ 3 -Cl)] + cores, respectively, surrounded by three bridging μ-dppa ligands Graphical Abstract Syntheses and Structures of Trinuclear Trigonal-bipyramidal Silver(I) Complexes with Bis(diphenylphosphino)amide Ligands

Reactions of [Et 4 N] 2 [WSe 4 ] with two equivalents of [Cu X ] powder gave trinuclear linear compounds [Et 4 N] 2 [(μ-WSe 4 )(Cu X ) 2 ] ( X = Cl 1, Br 2). Treatment of 1 or 2 with PPh 3 in CH 2 Cl 2 resulted in the formation of tetranuclear cubane-like compounds (μ 3 - X )(μ 3 -WSe 4 )(CuPPh 3 ) 3 ( X = Cl 3, Br 4). The structures of the heterobimetallic selenium compounds 1 and 4 ・ MeCN were confirmed by single-crystal X-ray diffraction. The nonlinear optical properties of 1 were investigated at λ = 532 nm with a pulse width of 7 ns Graphical Abstract Structural Transformation from Trinuclear Linear to Tetranuclear Cubane Heterobimetallic Selenium Compounds. Structure and Optical Linearities of [Et 4 N] 2 [(μ-WSe 4 )(CuCl) 2 ]

A new method for prediction of fundamental physical properties of ionic liquids (ILs) is proposed. The Residual Volume Approach (RVA) allows the estimation of density and viscosity of unknown ILs, using a simple linear correlation between a given property and a newly defined substituent parameter β X . The proposed method has been developed for the density estimation of 50 n -alkyl-substituted imidazolium and tetraalkylammonium salts in a homologous series of ILs and has been extended for the estimation of viscosity, which also correlates linearly with the corresponding β X . In addition, the parameters β X are temperature and pressure independent, which allows the prediction of these values at any temperature and pressure Graphical Abstract Simple Prediction of Some Physical Properties of Ionic Liquids: The Residual Volume Approach

The supersilylated ethene trans-(tBu 3 Si)HC=CH(SitBu 3 ) (triclinic, P ī) is accessible from the reaction of tBu 3 SiCHBr 2 with nBuLi at −78 °C in THF or Et2 O. The reaction of Li(H 2 NCH 2 CH 2 NH 2 )C≡CH with tBu 3 SiBr leads to the formation of (tBu 3 Si)C≡CH and (tBu 3 Si)C≡C(SitBu 3 ). X-Ray quality crystals of (tBu 3 Si)C≡C(SitBu 3 ) (triclinic, P ī) were obtained by recrystallization from hexane. In contrast to the structures of the disilane tBu3Si-SitBu3 and the disiloxane tBu 3 Si-O-SitBu 3 , the sterically crowded ethene trans-(tBu 3 Si)HC=CH(SitBu 3 ) and ethyne (tBu 3 Si)C≡C(SitBu 3 ) feature dihedral angles of 60° in the solid-state structures Graphical Abstract Supersilyliertes Ethen trans-(tBu 3 Si)HC=CH(SitBu 3 ) und Ethin (tBu 3 Si)C≡C(SitBu 3 ) / Supersilylated Ethene trans-(tBu 3 Si)HC=CH(SitBu 3 ) and Ethyne (tBu 3 Si)C≡C(SitBu 3 )

Antipyryl-arylamino-squaraines (11a -w) have been prepared by condensation of 3-antipyryl-4- hydroxy-cyclobutenedione (9a) with the primary aromatic amines 10a -w, using preferentially EtOH as the reaction medium. Surprisingly, 3-antipyryl-4-hydroxy-cyclobutenedione (9a) and 4-aminoantipyrine (13), under similar conditions, yielded 3-antipyryl-4-antipyrylamino-cyclobutenedione (14a), and not the expected squaraine. Reactions of 9a with the o-phenylenediamines 16a and 16b afforded the quinoxalines 17a and 17b, respectively Graphical Abstract Oxokohlenstoffe und verwandte Verbindungen. 33 [1]. Über die Umsetzung von 3-Antipyryl-4-hydroxy-cyclobutendion mit Aminen: Antipyryl-arylamino-quadraine – eine neue Klasse von C,N-Quadrainen / Oxocarbons and Related Compounds. 33 [1]. On the Reaction of 3-Antipyryl-4-hydroxy-cyclobutenedione with Amines: Antipyryl-arylamino-squaraines – a New Class of C,N-Squaraines

Graphical Abstract Synthetic and Cytotoxic and Antimicrobial Activity Studies on Annomuricatin B

Nine new 3-(3-chlorobenzyl)-5-arylidenefuran-2(5H)-ones were prepared in 20 - 87% yields by reaction of 3-(3-chlorobenzyl)furan-2(5H)-one with pertinent aldehydes. All compounds were fully characterized by IR and NMR spectroscopy as well asMS spectrometry. The phytotoxic properties of the synthesized lactones were evaluated as the ability to interfere with the growth of Sorghum bicolor and Cucumis sativus seedlings at 10 ppm and 100 ppm. Lactone 12, at 10 ppm, was the most active and selective, inhibiting the S. bicolor and C. sativus root growth by 70.7% and 10.7%, respectively. At 10 ppm, lactone 14 caused the larger effect on the inhibition (41.9%) of C. sativus. In general, the results indicate the influence of the benzylidene ring substitution on the phytotoxic activity Graphical Abstract Phytogrowth Activity of 3-(3-Chlorobenzyl)-5-arylidenefuran-2(5H)-ones

A new flavone glycoside, 6-hydroxyluteolin 7-O-[6 m -benzoyl-β -D-glucopyranosyl-(1 → 2)]-β - D-glucopyranoside (aphyllanthoside, 1) was isolated from the MeOH extract of the aerial parts of Globularia aphyllanthes. Besides this new compound, two flavonoid glycosides (6-hydroxyluteolin 7-O-[6 m -(E)-caffeoyl-β -D-glucopyranosyl-(1 → 2)]-β -D-glucopyranoside and isoquercitrin), three phenylethanoid glycosides (verbascoside, rossicaside A, and trichosanthoside A), and 11 iridoid glycosides (aucubin, catalpol, 10-O-benzoylcatalpol, globularin, asperuloside, besperuloside, asperulosidic acid, daphylloside, scandoside, alpinoside and baldaccioside) were also obtained and characterized. Identification of the isolated compounds was carried out by spectroscopic analysis including 1D and 2D NMR experiments as well as HRMS Graphical Abstract Flavonoid, Phenylethanoid and Iridoid Glycosides from Globularia aphyllanthes