Inorganic Chemistry Communications (v.9, #8)

Contents List (iii-x).

The reaction product of fac-[RuCl3(NO)(dppm)] with the 2-mercaptopyridine (pyS) ligand in methanol is the nitrosyl derivative with biphosphine monoxide [Ru(pyS)2(NO)(dppmO-P)]PF6. Elemental, spectroscopic and electrochemical analyses agree well with the proposed formulae.The reaction product of fac-[RuCl3(NO)(dppm)], dppm = bis(diphenylphosphino)methane with the 2-mercaptopyridine ligand (pyS) in methanol, in the presence of triethylamine, is the nitrosyl derivative [Ru(pyS)2(NO)(dppmO-P)]PF6 (1). In this reaction the ‘pyS’ ligand displaces one of the phosphorus atoms of the dppm moiety and this dangling phosphorus is oxidized in the experimental conditions generating a mono–hapto dppmO. The X-ray crystal structure of the complex [ Ru(pyS) 2 ( NO ) ( dppmO-P ) ] Cl · 1 2 H 2 O (2) shows sulfur atoms mutually trans and NO and P ligands trans to the pyridinic nitrogens. The ν NO band in the IR spectrum is at 1882 cm−1 and in the cyclic voltammogram two processes at −0.45 and −1.15 V (vs Ag/AgCl) are observed indicating a nitrosonium character for the coordinated NO.
Keywords: Nitrosyl; Ruthenium complexes; DppmO; 2-Mercaptopyridine; Cyclic voltammetry; X-ray structure;

The reaction of WO2(acac)2 with bis(3-hydroxypropyl)sulfide yields a novel octatungstate-supported molecular cluster [W8O19L3(acac)4] (L =  O (CH2)3S(CH2)3O; acac = acetylacetonate), which exhibits an unprecedented polyoxotungstate mode. Synthesis, formation of the cluster and its structure are discussed.A new polyoxotungstate cluster [W8O19L3(acac)4] (L =  O(CH2)3S(CH2)3O ; acac = acetylacetonate), was synthesized and characterized by single-crystal X-ray diffraction. The structure of the octatungstate cluster exhibits a novel unprecedented polyoxotungstate mode.

A novel trinuclear cobalt(III) phosphate complex, {[Co(en)2]3(PO4)(HPO4)}2(H2PO4)Cl7  · 6H2O, has been synthesized by reacting trans-dichlorobis(ethylenediamine)cobalt(III) chloride with disodium hydrogen phosphate in water.A novel trinuclear cobalt(III) phosphate complex, {[Co(en)2]3(PO4)(HPO4)}2(H2PO4)Cl7  · 6H2O, has been synthesized and characterized by single crystal X-ray structure determination and NMR spectroscopy. The compound includes an unprecedented type of discrete cluster with three metal atoms bridged by two phosphate anions. The clusters are associated in chains by strong hydrogen bonds PO4⋯H⋯PO4. The crystal lattice is stabilized by extensive hydrogen bonding.
Keywords: Cobalt(III); Coordination chemistry; Crystal structure; Ethylenediamine; Phosphate; NMR spectroscopy;

(H2NCH2CH2NH2)0.5MnSeO3 displays a hybrid structure in which the ethylenediamine acts as a pillar, linking inorganic sheets built up from edge and vertex-sharing MnO5N octahedra and SeO3 pyramids. The high-spin Mn2+ cations order antiferromagnetically at 18 K.(H2NCH2CH2NH2)0.5MnSeO3 displays a hybrid structure in which the ethylenediamine acts as a pillar, linking inorganic sheets built up from edge and vertex-sharing MnO5N octahedra and SeO3 pyramids. The high-spin Mn2+ cations order antiferromagnetically at 18 K.
Keywords: Hybrid solids; Manganese; Selenium; Magnetism;

Bulky rhodium diimine complexes for the catalyzed borylation of vinylarenes by Stephen J. Geier; Erin E. Chapman; Daniel I. McIsaac; Christopher M. Vogels; Andreas Decken; Stephen A. Westcott (788-791).
We have prepared and characterized fully three novel rhodium complexes containing a bulky diimine ligand to be used as catalysts for the borylation of vinylarenes. Reactions with B2pin2 (pin = 1,2-O2C2Me4) give the corresponding alkenylboronate esters in high yields.Rhodium(I) complexes containing the bulky diimine ligand (2,6-i-Pr2C6H3)DAB (DAB = 1,4-diaza-1,3-butadiene) have been prepared and characterized fully. The zwitterionic complex Rh(η6-catBcat){(2,6-i-Pr2C6H3)DAB} (3) was prepared in high yield by addition of B2cat3 to Rh(acac){(2,6-i-Pr2C6H3)DAB} (2). These rhodium complexes have been examined for their ability to catalyze the borylation of vinylarenes.
Keywords: Borylation; Catalysis; Diimine; Rhodium; Zwitterion;

The new 15-metallacrown-5 complexes [LnNi5(picha)5](NO3)3 (where Ln = Ce, Pr, Sm, Dy, Er and picha is 2-picolinehydroxamate) have been synthesised and characterised. The X-ray crystal structures of pyridine adduct of the Sm(III) complex, [SmNi5(picha)5(py)8(NO3)2](NO3), as well as of the analogous Pb(II) derivative [PbNi5(picha)5(py)11](OAc)2 have been determined. The cavity of the 15-metallacrown-5 can adjust to the size of the central metal ion by changing spin state of one of the peripheral Ni(II) ions.The new 15-metallacrown-5 complexes were synthesised from nickel(II) salts and 2-picolinehydroxamic acid in the presence of lanthanide(III) (Ce, Pr, Sm, Dy, Er) or lead(II) ions. The samarium(III) and lead(II) 15-metallacrown-5 complexes were obtained as pyridine adducts and their X-ray crystal structures were determined. In the case of samarium(III) derivative, four nickel(II) ions of the metallamacrocycle are high-spin, six-coordinate and one nickel(II) ion is low-spin, square-planar. In the case of the analogous derivative of the larger lead(II), all five peripheral nickel(II) ions are six-coordinate, which results in the enlargement of cavity size of the metallacrown. The reaction of nickel 15-metallacrown-5 samarium(III) complex with copper(II) ions leads into more stable copper 15-metallacrown-5 samarium(III) complex, as shown by 1H NMR and ESI-MS spectra.
Keywords: Metallacrowns; Lanthanide complexes; Lead complexes; Nickel complexes; Crystal structure;

In this paper, the new biferrocenamine-base receptor FcL was prepared and characterized. The X-ray crystal structure of FcL was also described. It belongs to monoclinic system P21/n space group, a  = 7.7113(1 5) Å, b  = 10.329(2) Å, c  = 18.753(4) Å, α  = 90°, β  = 98.52(3)°, γ  = 90°, V  = 1477.2(5) Å3, Z  = 2. The electrochemical studies reveal that the FcL show different redox processes (labelled with I, II, III) occurring at different potentials. The process III is quite an unexpected result, so we give rise to the assumption. Besides, the main interest in the receptors is that FcL show a two-wave behavior for Cu2+, Zn2+ and Ni2+, but was unresponsive to Mg2+ and Ca2+, suggesting that there is a selective sensing response.The new biferrocenamine-base receptor FcL was prepared and characterized. The X-ray crystal structure of FcL was also described. The electrochemical studies reveal that the FcL show a two-wave behavior for H+, Cu2+, Zn2+ and Ni2+, but was unresponsive to Mg2+ and Ca2+. The maximum oxidation peak potential shift of about 250 mV was found for FcL in the presence of Cu2+, Zn2+ or Ni2+.
Keywords: Ferrocenyl receptor; Crystal structure; Electrochemistry; Molecular recognition;

A highly selective Ru-based chemosensor for fluoride ion by Yonggang Zhao; Zhihua Lin; Shengju Ou; Chunying Duan; Haiping Liao; Zhiping Bai (802-805).
A highly selective fluorogenic signaling fluoride-sensor through an excited-state intermolecular proton transfer (ESPT) signaling transduction mechanism was obtained and structurally characterized.A highly selective fluorogenic signaling fluoride-sensor Ru-HL, comprised of Ru-bipy moiety (bipy = 2,2′-bipyridine) and 3-hydroxyl-2-naphthoylhydrazine was prepared and structurally characterized. The fluorescence spectra titration revealed the high selectivity and sensitivity of Ru-HL for F through an excited-state intermolecular proton transfer (ESPT) signaling transduction mechanism.
Keywords: Fluorescent sensor; Ru-bipy moiety; Fluoride ion; ESPT;

Easy access to chiral penta- and hexacoordinate silicon compounds by Uwe Böhme; Sebastian Wiesner; Betty Günther (806-809).
O,N,O-ligands which contain exclusively one stereoisomer prepared from amino acids of the chiral pool allow access to chiral penta- and hexacoordinate silicon complexes.Chiral penta- and hexacoordinate silicon complexes are accessible with O,N,O-ligands, which contain exclusively one stereoisomer prepared from amino acids of the chiral pool.
Keywords: Hypercoordinate; Chiral silicon; Complexes;

Dimerization of a highly unsymmetrical lutetium bisphthalocyanine in solution by Arnaud Mentec; Annig Pondaven; Jean-Michel Kerbaol; Maurice L’Her (810-813).
A lutetium heteroleptic bisphthalocyanine, bearing 16 chlorine atoms on one of the two macrocyclic rings and 4 tBu groups on the second phthalocyanine unit, dimerizes in dichloromethane or toluene solutions under ambient conditions.A lutetium heteroleptic bisphthalocyanine, bearing 16 chlorine atoms on one of the two macrocyclic rings and 4 tBu groups on the second phthalocyanine unit, dimerizes in dichloromethane or toluene solutions under ambient conditions.
Keywords: Lutetium sandwich complexes; Heteroleptic bisphthalocyanines; Dimerization; Solution;

Formation of the { Cu 3 II ( μ 3 -OH ) } 5 + core in copper(II) carboxylate chemistry via use of di-2-pyridyl ketone oxime [(py)2CNOH] : [Cu3(OH)(O2CR)2{(py)2CNO}3] (R = Me, Ph) by Theocharis C. Stamatatos; Jina C. Vlahopoulou; Yiannis Sanakis; Catherine P. Raptopoulou; Vassilis Psycharis; Athanassios K. Boudalis; Spyros P. Perlepes (814-818).
The use of di-2-pyridyl ketone oxime in reactions with CuII carboxylate sources has led to triangular complexes containing the { Cu 3 II ( μ 3 -OH ) } 5 + core and possessing the shown, very rare inverse 9-metallacrown-3 motif created by the bridging oximate groups; the complexes have interesting magnetic and EPR properties.Reactions of [Cu2(O2CMe)4(H2O)2] or Cu(O2CPh)2  · 2H2O with 2 or 1, respectively, molar equivalents of di-2-pyridyl ketone oxime, (py)2CNOH, in MeCN-based solvent mixtures yield complexes [ Cu 3 II ( μ 3 -OH ) ( O 2 CR ) 2 { ( py ) 2 CNO } 3 ] (1, R = Me; 2, R = Ph). Crystal structures of these compounds show similar triangles of CuII ions, centered by a triply bridging hydroxo ligand and with three edge-bridging oximate groups from the three 2.1110 (py)2CNO ions. Preliminary variable-temperature magnetic susceptibility studies and EPR data at 4.2 K for 1 reveal an antiferromagnetically-coupled system showing antisymmetric exchange.
Keywords: Antisymmetric exchange; Copper(II) triangles; Di-2-pyridyl ketone oximate complexes; EPR spectra; Triply-bridging (μ3) hydroxide;

A novel 3D hybrid architecture based on (H2O)6 encircling Cu4I4–O–Cu4I4 cluster and hexanuclear Cu6(datrz)6 ring by Quan-Guo Zhai; Can-Zhong Lu; Shu-Mei Chen; Xin-Jiang Xu; Wen-Bin Yang (819-822).
A novel three-dimensional hybrid solid, [(H3O)2(H2O)4] [{Cu6(datrz)6}{(Cu4I4)2O}] (1), consisting of two kind of unique six-connected SUBs: dumb-like Cu4I4–O–Cu4I4 clusters and hexanuclear Cu6(datrz)6 rings, were synthesized and characterized.The reaction of ligand datrz (3,5-diamino-1,2,4-triazole) with CuI in 1:1 ethanol and water mixed solvent under solvothermal condition gives a novel three-dimensional hybrid solid, [(H3O)2(H2O)4][{Cu6(datrz)6}{(Cu4I4)2O}] (1), which consists of unique six-connected dumb-like Cu4I4–O–Cu4I4 clusters and hexanuclear Cu6(datrz)6 rings. Interestingly, the chair-form water hexamer is firstly observed being interpenetrated by the inorganic cluster.
Keywords: Hybrid organic–inorganic materials; CuI; 1,2,4-Triazole; Solvothermal synthesis;

Arylid-Box: A new family of chiral bis-oxazoline ligands for metal mediated catalytic enantioselective synthesis by Elisabete da Palma Carreiro; Serghei Chercheja; Nuno M.M. Moura; Cláudia S.C. Gertrudes; Anthony J. Burke (823-826).
A series of novel bis-oxazoline ligands with an unusual arylidene back-bone, (appropriately abbreviated to Arylid-Box) have been prepared and used to form Cu(I) complexes in situ for the catalytic asymmetric cyclopropanation of styrene and α-methylstyrene under a variety of conditions. Enantiomeric excesses as high as 89% were obtained.A new family of chiral non-racemic bis-oxazolines containing an arylidene bridging unit (and appropriately termed Arylid-Box) have been prepared from malonate esters in satisfactory yields. These ligands have been screened in the Cu(I) catalysed enantioselective cyclopropanation of styrene and α-methylstyrene with ethyl diazoacetate giving enantioselectivities of up to 89% ee. The tBu substituted ligands (2d, 3d and 4d) gave the best ees. Our experiments seemed to indicate that there was no overall dependency of the reaction stereoselectivity or efficiency on reaction conditions, like, solvent, counter ion or temperature.
Keywords: Asymmetric catalysis; Enantioselectivity; Bis-oxazoline; Cyclopropanation; DFT study;

The complex PtII(cyclooctatetraene)(CN)2 shows a longest-wavelength absorption (λ max  = 430 nm) which is assigned to a (PtII  → π C8H8) MLCT transition. At r.t. the solid complex displays an intense orange emission at 572 nm which originates from the MLCT triplet. The emission spectrum exhibits a vibrational structure which may indicate an IL contribution.The complex PtII(cyclooctatetraene)(CN)2 shows a longest-wavelength absorption (λ max  = 430 nm) which is assigned to a (PtII  → π C8H8) MLCT transition. At r.t. the solid complex displays an intense orange emission at 572 nm which originates from the MLCT triplet. The emission spectrum exhibits a vibrational structure which may indicate an IL contribution.
Keywords: Electronic spectra; MLCT; IL; Phosphorescence; Platinum complexes; Cyclooctatetraene complexes;

The complex [Ir(azulene)(1,5-cyclocta-diene)]+ shows long-wavelength absorptions which are assigned to spin-allowed (λ max  = 536 nm) and spin-forbidden (675 nm) transitions. They are of mixed MLCT (Ir → azulene) and ILCT (azulene) character. At 77 K the solid complex displays an emission (λ max  = 816 nm) which originates from the MLCT/ILCT triplet. At r.t. in solution the complex undergoes a photosubstitution of the azulene ligand. It is suggested that in the CT state the azulene ligand looses its coordinating ability.The complex [Ir(azulene)(1,5-cyclocta-diene)]+ shows long-wavelength absorptions which are assigned to spin-allowed (λ max  = 536 nm) and spin-forbidden (675 nm) transitions. They are of mixed MLCT (Ir → azulene) and ILCT (azulene) character. At 77 K the solid complex displays an emission (λ max  = 816 nm) which originates from the MLCT/ILCT triplet. At r.t. in solution the complex undergoes a photosubstitution of the azulene ligand. It is suggested that in the CT state the azulene ligand looses its coordinating ability.
Keywords: Electronic spectra; MLCT; ILCT; Luminescence; Photochemistry; Iridium; Azulene;

The analysis of intermolecular interactions in the crystal structure of dichloro(2-hydroxy-1-naphtaldehyde-3-methylisothio semicarbazonato) iron(III) indicates the significance of a unique multistacked π, π interaction between five and six membered chelate rings of the adjacent molecules for the association of molecules in the solid state.Dichloro(2-hydroxy-1-naphtaldehyde-3-methylisothio semicarbazonato) iron(III) contains structural fragments capable for formation of hydrogen bonds and π stacking interactions. The analysis of intermolecular interactions in the crystal structure indicates the significance of a unique multistacked π, π interaction between five and six membered chelate rings of adjacent molecules in chains extended along the b axis.
Keywords: Metalloaromaticity; Chelate/chelate π, π stacking interaction; Thiosemicarbazonato iron(III) complex;

Benzoic acid inclusion in a dimeric nickel complex and its catalytic activity by Anirban Karmakar; Kaustavmoni Deka; Rupam J. Sarma; Jubaraj B. Baruah (836-838).
A benzoic acid included aquo-bridged di-nuclear nickel benzoate complex is reported. Analogous compound from nitro-benzoate could not be prepared from solution. The composition of pyridine containing nickel nitrobenzoate complexes are governed by the position of the nitro group on the aromatic ring. The dimeric nickel complex is an excellent catalyst for esterification reactions.Intrinsic acidity of benzoic acid included in nickel complex can contribute to catalytic activity for esterification reactions.
Keywords: Nickel benzoate complexes; Substituent effect; Hydrogen-bonding; Catalyst; Esterification;

An unprecedented 1D ladder-like silver(I) coordination polymer with ciprofloxacin by Zhen-Feng Chen; Liang-Cai Yu; Di-Chang Zhong; Hong Liang; Xu-Hui Zhu; Zhong-Yuan Zhou (839-843).
A 1D ladder-like silver(I) coordination polymer, {[Ag4(H-Cip)2(Cip)2 (NO3)2] · 4H2O} n (1) was synthesized and structurally characterized. 1 consists of pseudo-tetra-nuclear silver building blocks constructed via monodentate H-Cip and tetradentate depronated Cip ligands. In the solid state, 1 displays an emission maximum at 410 nm at room temperature.A 1D ladder-like silver(I) coordination polymer, {[Ag4(H-Cip)2(Cip)2(NO3)2] · 4H2O} n (1) (H-Cip = ciprofloxacin, Cip = depronated ciprofloxacin) was synthesized and structurally characterized. 1 consists of pseudo-tetra-nuclear silver building blocks constructed via monodentate H-Cip and tetradentate depronated Cip ligands. In the solid state, 1 displays an emission maximum at 410 nm at room temperature, apparently originated from the intraligand excited states.
Keywords: Silver; Ciprofloxacin; Crystal structure; Coordination polymer; Photoluminescence;

A novel 3-D coordination polymer [Cd2(pydc)2(H2O)]n (pydc = pyridine-2,3-dicarboxylate) 1 has been hydrothermally synthesized. It consists of two kinds of Cd(II) center with different coordination environments by pydc and aqua ligands, to form a 3-D open framework. 1 display strong fluorescent emission at room temperature.A novel 3-D coordination polymer [Cd2(pydc)2(H2O)] n (pydc = pyridine-2,3-dicarboxylate) 1 has been hydrothermally synthesized and characterized by the elemental analyses, IR spectrum and the single crystal X-ray diffraction. The title compound consists of two kinds of Cd(II) center with different coordination environments by pydc and aqua ligands, to form a 3-D open framework. Compound 1 display strong fluorescent emission in the solid state at room temperature.
Keywords: Synthesis; Crystal structure; Coordination polymer; Luminescent properties;

An unprecedented Cu(I)/Cu(II)/Pb(II)-containing coordination polymer, which comprises two single-stranded helical chains recognizing each other to generate molecular zipper structure and parallel double-stranded helices under the direction of supramolecular interaction, is synthesized hydrothermally and characterized.An unprecedented Cu(I)/Cu(II)/Pb(II)-containing coordination polymer, { Pb ( ip ) 2 [ Cu 2 II ( obpy ) 2 ] [ Cu 2 I ( obpy ) 2 ] } n ( H 2 O ) 2 n 1(ip = isophthalate, Hobpy = 6-hydroxy-2,2-bipyridine), which comprises two single-stranded helical chains recognizing each other to generate molecular zipper structure and parallel double-stranded helices under the direction of supramolecular interaction, is synthesized hydrothermally and characterized by IR, ICP, TG–DTA, and so on.
Keywords: Hydrothermal synthesis; Helical chain; ip; obpy; Molecular recognization; 4,4′-bpy;

During attempted preparation of [Co(NH3)6]Cl[Hg(SCN)4] from an aqueous mixture of [Co(NH3)6]Cl3 and (NH4)2[Hg(SCN)4], an unexpected highly crystalline product of composition [Co(NH3)6][Hg2(SCN)7] has been obtained in an excellent yield.The reaction of [Co(NH3)6]Cl3 with a mixture of HgCl2 and NH4SCN in 1:2:8 molar ratio in hot aqueous medium leads to formation of a new complex salt, [Co(NH3)6][Hg2(SCN)7] (1) in 70% yield. This hexaamminecobalt(III) complex salt has been characterized by elemental analyses, solubility measurement and spectroscopic techniques (e.g. UV/Visible, IR and 13C NMR). Single crystal X-ray structure determination of 1 revealed the presence of discrete [Co(NH3)6]3+ cation and a new anion, [Hg2(SCN)7]3−. This is the first report of a complex salt containing the new anion. The crystal lattice of the complex salt is stabilized by electrostatic forces of attraction and N–H…N (thiocyanate) hydrogen bonding interactions.
Keywords: Cobalt(III); Coordination chemistry; Second sphere coordination; Spectroscopy; X-ray crystallography;

View of one 3D microporous framework with rare 42638 topology.Herein, one metallic–organic coordinated polymer, namely Cd2(bpp)32-Cl)2(μ-Cl)2 (1) (bpp = 1,3-bis(4-pyridyl)propane) was synthesized hydrothermally by the reaction of bpp ligands with CdCl2, possessing the 3D 2-fold interpenetrating nets with the rare four-connected sra-type zeolite topology. Further, the luminescent and thermal stability characters are investigated, and the results reveal that they could to be potential, microporous and fluorescent materials.
Keywords: Hydrothermal synthesis; bpp; Interpenetration; sra-type; Topology;

The titanium complexes described herein were synthesized with high yields. After MAO activation they provide high or ultra-high molar mass polyethene with moderate catalytic activities.In this work titanium dichloro complexes bearing diethylmalonate, diethylphenylmalonate and diphenylmalonate ligands have been synthesized. The complexes were activated by methylaluminoxane (MAO) and exhibited moderate activity [10–50 kgPE/(molTi  h bar)] in ethene polymerization. The catalysts produced ultra high molar mass polyethene (PE) (up to 3000 kg/mol) with polydispersity values range between 2 and 4.
Keywords: Titanium; Malonate; MAO; Ethene polymerization;

Synthesis and characterization of Zn(II) and Cd(II) complexes with 2,6-diacetylpyridine-bis(selenosemicarbazone). Crystal structure of a Ni(II) complex with a modified 2,6-diacetylpyridine-bis(selenosemicarbazone) by Tamara R. Todorović; Alessia Bacchi; Giancarlo Pelizzi; Nenad O. Juranić; Dušan M. Sladić; Ilija D. Brčeski; Katarina K. Andelković (862-865).
A ligand 2,6-diacetylpyridine-bis(selenosemicarbazone) was synthesized and coordinated with Zn(II), Cd(II) and Ni(II). With Zn(II) and Cd(II), the ligand was coordinated as a quinquedentate in a trigonal bipyramidal geometry. With Ni(II) the ligand was modified by elimination of H2Se and the product was coordinated as a quadridentate forming a square planar complex.A novel ligand 2,6-diacetylpyridine-bis(selenosemicarbazone) was synthesized and coordinated with Zn(II), Cd(II) and Ni(II). With Zn(II) and Cd(II), the bideprotonated ligand was coordinated as a quinquedentate in trigonal bipyramidal geometry. With Ni(II) during coordination the ligand was modified by elimination of hydrogen selenide and the product was coordinated as a quadridentate forming a square planar complex, the structure of which was determined by X-ray analysis.
Keywords: Selenosemicarbazone derivatives; Zn(II), Cd(II), Ni(II) complexes; X-ray analysis; NMR spectroscopy;

The solid compound Ag(binap)NO3 with binap = 2,2′-bis(diphenylphosphino)-1,1′-binaphthyl shows an IL phosphorescence at λ max  = 510 nm under ambient conditions. The silver–phosphine bonding is sufficiently covalent to transmit the heavy-atom effect of silver to the binaphthyl chromophore.The solid compound Ag(binap)NO3 with binap = 2,2′-bis(diphenylphosphino)-1,1′-binaphthyl shows an IL phosphorescence at λ max  = 510 nm under ambient conditions. The silver–phosphine bonding is sufficiently covalent to transmit the heavy-atom effect of silver to the binaphthyl chromophore.
Keywords: Electronic spectra; Intraligand excited states; phosphorescence; Silver complexes; Phosphine complexes; Heavy-atom effect;

Ni(II)-Mediated nitrosation of oximes bearing an α-CH2 group by Anastassiya V. Makarycheva-Mikhailova; Pavel V. Gushchin; Maximilian N. Kopylovich; Ilya N. Ganebnykh; Valery N. Charushin; Matti Haukka; Armando J.L. Pombeiro; Vadim Yu. Kukushkin (869-871).
Reaction of NiCl2  · 6H2O with an oxime having an α-CH2 group in air leads to the formation of the complexes [Ni(dioxime/ato)2] formed due to a novel type of metal-mediated nitrosation.Heating of NiCl2  · 6H2O with 10-fold excess of an oxime having an α-CH2 group (14) at 100 °C for 1 day in air leads to the formation of the dioxime/ato complexes [Ni(dioxime/ato)2] (58) formed due to a novel type of metal-mediated nitrosation. Compounds 58 were characterized by elemental analyses, FAB (57) or APCI (8) mass-spectrometry, IR, 1H and 13C{1H} spectroscopies (for 8), and X-ray structural study has been performed for 5 and 8; the corresponding ketones (912) were identified by LC–MS.
Keywords: Nickel(II); Oximes; Dioximes; Metal-mediated reaction; Nitrosation;

In this article, a Cu(I)–halide complex [Cu(II)3Cu(I)4(NA)6 Br4]n (complex 1) has been synthesized under hydrothermal reaction conditions. Complex 1 is a two-dimensional layer structure composed by trinuclear Cu(II) unit and tetranuclear Cu(I) unit connected by NA (NA = nicotinate) ligands.In this article, a Cu(I)-halide complex [Cu(II)3Cu(I)4(NA)6Br4]n (complex 1) (NA = pyridine-3-carboxylate) has been synthesized under hydrothermal reaction conditions. Complex 1 is a two-dimensional layer structure composed by trinuclear Cu(II) unit and tetranuclear Cu(I) unit connected by NA ligands. Complex 1 exhibits strong luminescent property at room temperature.
Keywords: Mixed-valence Cu; Hydrothermal reaction; NA; Cu(I)–halide complex; Luminescent property;