Inorganic Chemistry Communications (v.7, #7)

Contents list (iii-v).

Synthesis of a serious of copper(II)-pyrazolyl complexes in different solvents and anions by Wei-Zheng Shen; Long Yi; Peng Cheng; Shi-Ping Yan; Dai-Zheng Liao; Zong-Hui Jiang (819-822).
After obtaining a mononuclear complex [Cu(Hpz)4SO4](H2O) (1) (Hpz=pyrazole) through the reaction of CuSO4  · 5H2O and pyrazole in water solution, we repeated the synthesis process in methanol solution and got an unexpected 1D complex [Cu(Hpz)4SO4] n (CH3OH) n (2), which has the same [Cu(Hpz)4SO4] unit but different coordination motif with 1. While we used Cu(ClO4)2  · 6H2O in the synthesis system of 2, a rarely cyclic tri-nuclear copper(II) complex [Cu33-O)(pz)3(Hpz)312-ClO4)](CH3OH) (3) was obtained. The Cu33-O)(pz)3 unit in 3 consists of an almost flat Cu3N6 ring and a pyramidal Cu3O group with the average Cu–O distances of 1.998 Å and the average Cu–O–Cu angle of 108°. Complexes 13 were characterized by X-ray structural analysis and ESR spectra.
Keywords: Pyrazole; Copper(II) complexes; 1D chain; Cyclic tri-nuclear; ESR;

MO3  ·  nH2O when dissolved in H2O2 reacts with QOH (8-quinolinol) affording MO(O2)2  · 2QOH wherefrom [MO(O2)(QO)2] [M=Mo (1) and W (2)] is obtained during crystallization and the synthesis and structure of 2 is reported here for the first time. Using both 1and 2 as catalyst precursor and H2O2, O2 or H2O2  + O2 as oxidant, benzyl and cinnamoyl alcohol, cyclohexanol and isopropanol are selectively oxidized to their corresponding aldehydes and ketones, but this selectivity is not strictly exhibited when substrates are aliphatic alcohols.
Keywords: Oxoperoxo-molybdenum and -tungsten; Crystal structure; Catalytic oxidation; Alcohol to aldehyde conversion; Sulfide to sulfone conversion;

Spectroscopic studies revealed that the ligand 2-(2-hydroxyphenyl)-1,3-benzoxazin-4-one (1) exhibited a rather high selectivity for the Zn2+ cation. The quantum yield of 1 was increased by about 180-fold upon addition of an excess of Zn2+ at the emission maximum of 506 nm upon excitation at 406 nm. Coordination of 1 to Zn2+ ions led to the isolated complex 2 having a 1:1 stoichiometry and exhibiting characteristic modifications in the absorption and NMR spectra.
Keywords: Zinc (II) complex; Fluorescence; UV–Vis; Oxazin ring;

The new [(3-carboxy-5-methyl-1H-1-pyrazolyl) (3-methyl-5-carboxy-1H-1-pyrazolyl)methane], CH2(PzCOOH,Me)(PzMe,COOH), and bis(3-carboxy-5-methyl-1H-1-pyrazolyl)methane, CH2(PzCOOH,Me)2, ligands are prepared in CH2Cl2/H2O solution using the ethyl 3-methylpyrazole-5-carboxylate, an excess of Na2CO3, and benzyltriethylammonium chloride as the phase transfer catalyst. The CH2(PzCOOH,Me)2 ligand reacts with ZnAc2 and CdCl2 in the presence of two equivalents of NaOH, to yield the {M[CH2(PzCOOH,Me)2] ·  nH2O} (M=Zn(II), n=2; M=Cd(II), n=1) complexes. All compounds have been fully characterized by elemental analyses and FT-IR in the solid state and by NMR (1H, 13C, and 113Cd) spectroscopy and electrospray ionization mass spectrometry in solution. The complexes likely contain a five- or six-coordinate metal core in which the ligand is coordinated to the metal ions in the κ4-N,N ,O,O fashion.
Keywords: Water soluble bis(pyrazolyl)methane ligands; Zinc(II); Cadmium(II); Electrospray mass spectrometry;

Linear dependence between the energy maxima of the charge transfer (CT) bands simulated from the singlet excited states, calculated using TD CPCM, and the energy maxima of the experimental CT bands from the absorption spectrum of [Ru(bpy)2(CN x )Cl]+ in seven solvents of different polarity was used to produce calculated spectra that correlate very well with experiment.
Keywords: Density functional theory; Time dependent density functional theory; Conductor-like polarizable continuum model; Solvatochromism; Ruthenium (II) heterocycle; Isocyanide complex;

Chirality in cyclotriphosphazenes with one stereogenic centre by Serap Beşli; Simon J. Coles; David B. Davies; Robert J. Eaton; Michael B. Hursthouse; Adem Kılıç; Robert A. Shaw; Aylin Uslu; Serkan Yeşilot (842-846).
Mono-substitution reactions of gem symmetrically disubstituted cyclophosphazenes such as (1) and (2) provide a convenient way to investigate the chiral configurational properties of cyclophosphazene compounds with one stereogenic centre. Previous work by X-ray crystallography has shown that the mono-dibenzylamino derivative of (1), compound (3a), is chiral and exists as a racemate. In this work, compound (1) was reacted with piperidine, dimethylamine, pyrrolidine and phenol to give compounds (3b3e), respectively, and compound (2) was reacted with dimethylamine to give (4). The structures and stereogenic properties of new compounds (3b), (3c) and (4) were determined by X-ray crystallography and, together with compound (3a), the chirality was confirmed by 31P NMR spectroscopy on addition of a chiral solvating agent (CSA), (S)-(+)-2,2,2-trifluoro-1-(9-anthryl)ethanol. As compound (3d) did not give crystals suitable for X-ray crystallography and compound (3e) is an oil, their stereogenic properties were confirmed by 31P NMR spectroscopy on addition of CSA. The work confirms that cyclophosphazene derivatives containing one centre of chirality exist as racemates and shows that the chiral properties of such molecules may be determined by 31P NMR spectroscopy on addition of a chiral solvating agent in those cases where X-ray crystal structures are not available.
Keywords: Cyclotriphosphazene derivatives; Chirality; Crystal structures; NMR; CSA (chiral solvating agent);

Photochemical synthesis of Bi2S3 nanoflowers on an alumina template by Wen-Bo Zhao; Jun-Jie Zhu; Jin-Zhong Xu; Hong-Yuan Chen (847-850).
Bismuth sulfide (Bi2S3) nanoflowers have been successfully prepared on a alumina template by a photochemical method from an aqueous solution of bismuth nitrate (Bi(NO3)3) and thioacetamide (TAA) in the presence of complex agent of nitrilotriacetic acid(NTA) at room temperature.
Keywords: Photochemical synthesis; Bismuth sulfide; Crystal structure; Characterization;

Hydrothermal reactions of fumaric acid, 1,10-phenanthroline or 2,2-bipyridine and transition metal cations gave rise to two complexes, [Zn(Hmal)(1,10-phen)(H2O)] n (1) and [Cu(Hmal)(2,2-bipy)] n  · 3nH2O (2) (malic acid=H3mal). The photoluminescence spectrum and the interesting second-order non-linear optical (NLO) property for compound 1 have been studied.
Keywords: Transition metal complex; Mixed ligands; Photoluminescence; NLO;

Unique photoreactivity of mercury(II) 5,10,15,20-tetrakis(4-sulfonatophenyl)porphyrin by Ottó Horváth; Zsolt Valicsek; Arnd Vogler (854-857).
Deviating from coplanar metalloporphyrins, the photochemistry of the kinetically labile, sitting-atop mercury(II) 5,10,15,20-tetrakis(4-sulfonatophenyl)porphyrin complex is characterized by irreversible porphyrin ligand to metal charge transfer and reversible dissociation.
Keywords: Photophysics; Photochemistry; Charge transfer; Dissociation; Metalloporphyrin; Mercury;

Ferromagnetic linear trinuclear copper (II) complex bridged by sulfosalicylate ligand by Wen-Guo Wang; Jie Zhang; Li-Jun Song; Zhan-Feng Ju (858-860).
A sulfosalicylate-bridged linear trinuclear Cu(II) complex [Cu3(SSA)2(Bpy)2(H2O)4] · 4H2O, where SSA is sulfosalicylate anion, is synthesized and structurally characterized. A ferromagnetic coupling between adjacent copper ions dominates the magnetic property of this complex.
Keywords: Copper (II) complex; Trinuclear; Sulfosalicylate; Magnetic;

A new hybrid germanium vanadate (2,2-bpy)2(VVO2)2(H2GeO4) · 6H2O 1 (2,2-bpy=2,2-bipyridine) was synthesized by hydrothermal method and structurally characterized by single-crystal X-ray diffraction, thermogravimetric analysis (TGA), IR, XRD and elemental analyses. Crystal data for 1: monoclinic, C2/c, a=16.6937(9) Å, b=11.3501(6) Å, c=17.4774(9) Å, β=118.19(2)°, V=2918.7(3) Å3, Z=4. Compound 1 is composed of the first germanium vanadate skeleton covalently attached to 2,2-bpy ligands.
Keywords: Germanate; Vanadate; Inorganic–organic hybrid; Hydrothermal synthesis; Crystal structure;

A novel three dimensional (3D) polymer, [Co2(hypa)2(4,4-bipy)] (1) (H2hypa = hydroxy-phenyl-acetic acid, 4,4-bipy = 4,4-bipyridine), featuring pentacoordinate, dimeric cobalt(II) as subunits have been prepared, which shows low-dimensional antiferromagnetic ordering blow 15.2 K (T N).
Keywords: Pentacoordination; Antiferromagnetism; Cobalt(II); Hydrothermal synthesis;

An unprecedented, triply bridging sulfur atom of the dithiophosphate ligand was observed in the new silver cluster cation, Ag4(μ-dppm)2[S2P(OEt)2]3 +, where the coordination geometry for the trifurcated sulfur atom exhibited distorted seesaw.
Keywords: Clusters; Silver; Dithiophosphates; Bonding modes; Seesaw geometry;

The simple synthesis of stable A3- and trans-A2B-molybdenum(V) corrolates by Volodymyr Sashuk; Beata Koszarna; Piotr Winiarek; Daniel T. Gryko; Karol Grela (871-875).
An efficient synthesis of molybdenum(V) corrolates is detailed and some of their spectroscopic properties are described. Paramagnetic character of these complexes was confirmed by ESR measurements.
Keywords: Corroles; Molybdenum; Complexes;

The reaction of the mono-lacunary silicotungstate ligand α-K8SiW11O39  · 13H2O with praseodymiumIII cation results in a new Keggin-type derivative K3[(Pr(H2O)4SiW11O39)(NaPr2(H2O)12)(Pr(H2O)4SiW11O39)] · 13.5H2O (1), whose polyanion consists of two crystallographically distinct [Pr(H2O)4SiW11O39]5− building block units and one [NaPr2(H2O)12]7+ subunit, which are connected by alternating praseodymium and sodium centers via the terminal and bridging oxygen atoms from the precursor [α-SiW11O39]8− to construct a 1D infinitely chainlike structure.
Keywords: Polyoxometalate; Silicotungstate; Lanthanide; Heteropolycompound;

The asymmetric compartmental proligand HL bearing a tridentate N2O donor set and a bidentate OO donor set has given the novel heteronuclear [Ni(II)–Na] infinite chain polymer in which the molecular structure has a repeating Na/Ni5 unit of formula [Ni5Na(L)2(OAc)6(OH)2(BPh4)] n .
Keywords: Crystal structure; Heteronuclear nickel(II)–sodium complex; Chain polymer;

The first 1,3,2-diazaphospha-[3]ferrocenophanes by Bernd Wrackmeyer; Elena V. Klimkina; Wolfgang Milius (884-888).
1,1-Diaminoferrocene 1 reacts with tert-butyl-(2a) and phenylphosphorus dichloride (2b) in the presence of triethylamine to afford the respective 1,3,2-diazaphospha-[3]ferrocenophanes 3a and 3b, of which 3a could be isolated in good yield and high purity. The phosphane 3a reacts with bis(trimethylsilyl)peroxide to give the oxide 5a, and with sulfur and selenium to the sulfide (6a) and the selenide (7a), respectively. The molecular structures of 3a and 7a, as determined by X-ray analysis, show that the tert-butyl group is in cis-position relative to the N–H bond vectors. NMR spectra prove that prominent structural features are retained in solution.
Keywords: Aminophosphanes; [3]Ferrocenophanes; NMR; X-ray;

Hydrothermal syntheses and crystal structures of two lanthanum compounds La(OH)SO4 and LaO(NO3) by Quanzheng Zhang; Canzhong Lu; Wenbin Yang; Shumei Chen; Yaqin Yu (889-892).
Two three-dimensional lanthanum compounds La(OH)SO4 1 and LaO(NO3) 2 have been hydrothermally synthesized and characterized by single-crystal diffraction. Compound 1 represents the first example of hydroxide lanthanide sulfates. Compound 2 is a structural isomer of another previously reported LaONO3, however, its crystal structure is different from that of the compound.
Keywords: Lanthanum sulfate; Lanthanum nitrate; Hydrothermal syntheses; Crystal structure;

Synthesis, characterization and electrocatalytic behaviors of α-K6[As2W12Mo6O62] · 12H2O by Israel-Martyr Mbomekalle; Yu Wei Lu; Bineta Keita; Louis Nadjo (893-898).
Pure α-K6[As2W12Mo6O62] · 12H2O was synthesized for the first time. It was obtained in high yield by careful consideration of the main experimental parameters. Keys to the successful achievement of this synthesis include the high acidity of the medium, the order of addition of reactants, the necessity of keeping a larger than stoichiometric molybdate to lacunary polyoxometalates ratio during the synthesis and the recrystallization in fairly acidic medium. Purity of the isolated product was checked by elemental analysis, electrochemistry, IR spectroscopy, UV–Vis spectroscopy and 183W NMR spectroscopy. Comparison of the physical characteristics of α-K6[As2W12Mo6O62] · 12H2O with the corresponding ones of its known phosphorus analogue, α-K6[P2W12Mo6O62] · 14H2O, confirms that the two complexes have the same structure. The expected positive potential shift of the first several voltammetric waves linked with the presence of As instead of P as the central heteroatom in these molecules was observed. The behaviours of α-K6[As2W12Mo6O62] · 12H2O and α-K6[P2W12Mo6O62] · 14H2O in the electrocatalytic reduction of nitrous acid and nitrogen monoxide were studied and compared with each other and with the activity of α-K6[As2W18O62] · 14H2O.
Keywords: α-K6[As2W12Mo6O62] · 12H2O; α-K6[P2W12Mo6O62] · 14H2O; Wells–Dawson polyoxometalate; IR; 31P and 183W NMR; Nitrous acid; Nitrogen monoxide; Electrocatalysis;

Unusual (fulvene)chromiumcarbonyl complexes by Frank T Edelmann (899-902).
The preparation and characterization of several new and unusual (fulvene)chromiumcarbonyl complexes is reported. η6-Phenyl-coordinated iso-(6,6-diphenylfulvene)Cr(CO)3 (1) is obtained by treatment of (η6-benzophenone)Cr(CO)3 with cyclopentadiene. Tricarbonyl(1-fulvenyl-4,6,8-trimethylazulene)chromium(0) (3) is the first transition metal complex containing a tricyclic fulvenylazulene ligand. P-Coordination without participation of the fulvene ring system has been achieved in the complex (6,6-dimethyl-1-diphenylphosphinofulvene)Cr(CO)5 (4).
Keywords: Fulvenes; Fulvene complexes; Chromium complexes; Azulene; Carbonyl complexes;

In [Ru(bpy)2(CO)X] n -type complexes (bpy=2,2-bipyridine, X=CH3 or COCH3), chemical reactions with a proton and one-electron oxidation behavior have been described. In the present work, selective methyl group dissociation in the Ru–X moieties was exhibited.
Keywords: Ruthenium; Methyl group dissociation; Redox reaction; Reaction with proton;

A novel perchlorate-bridged tetranuclear zinc(II) structure with tris(2-aminoethyl)amine ligand by Heng Fu; Xue-Wen Liu; Zhong-Yuan Zhou; Zong-Wan Mao; Kang-Cheng Zheng; Xiao-Ming Chen (906-908).
A highly symmetric zinc(II) complex with{[Zn(tren)]44-ClO4)}7+ structure unit (tren=tris(2-aminoethyl)amine) was characterized by single-crystal X-ray diffraction and was understood by the calculation from the MNDO method.
Keywords: Crystal structure; Perchlorate-bridged; Zinc tetramer; MNDO calculation; Tris(2-aminoethyl)amine;

The new supermolecular structure of chain organic–inorganic hybrid compound {[Cu(phen)]2(VO2)(H2O)2(H2PO4)2 (PO4)} (phen=1,10-phenanthroline) by Yanjie Cui; Guanghua Li; He Meng; Yan Xing; Hong Ding; Jian Sun; Li Liu; Wenqin Pang (909-911).
A new organic–inorganic hybrid compound {[Cu(phen)]2(VO2)(H2O)2(H2PO4)2(PO4)} 1 has been synthesized hydrothermally. Single crystal X-ray diffraction revealed that the chain compound 1 consists of two vanadium-corner-shared [Cu–O–P–O–V–O] 6-membered rings {Cu2VP2O6}, which is further connected by {PO4} tetrahedra. This connected manner is rarely reported before. With significant π–π stacking between phen rings and hydrogen bonding contributing to inter-chain interactions, the 1D chains extend into a 3D supermolecular structure.
Keywords: Vanadium phosphate; Hydrothermal synthesis; Organic–inorganic hybrid; Chain; Supermolecular structure; Phen;

A novel compound Cu PZDC 2 ·3 H 2O ·2 IDZC n has been synthesized and its structure was determined by X-ray diffraction analysis, which consists of a 2,3-pyrazine dicarboxylate anion bridged crossing double chain running along a-axis.
Keywords: 2,3-Pyrazinedicarboxylic acid; Low-dimensional materials; Magnetic systems; Crystal;

Complex [Pb(BzImH)2py(H2O)2(NO3)2] · (BzImH)2py · H2O has been synthesized and characterized by IR-spectrum and CHN-elemental analysis. The crystal structure of this compound consists of monomeric units of [Pb(BzImH)2py(H2O)2(NO3)2] · (BzImH)2py · H2O. Each lead atom is chelating by the nitrogens of (BzImH)2py ligand and the oxygen atoms of nitrate anions and also the oxygen atoms of two water molecules. The Pb atom has an nine-coordinate geometry and around lead atoms is hemidirected.
Keywords: Lead(II) complexes; Crystal structures; 2,6-Bis(2-benzimidazolyle)pyridine ligand;

Mg2Gd8(SiO4)6O2 doped with Tb3+ was in situ synthesized by a novel hybrid precursors assembly sol–gel technology. The particle size of luminescent materials is in the range of 60–100 nm characterized by XRD and especially SEM shows that there exist some novel unexpected morphological structures owing to multicomponent hybrid precursors. The photoluminescence property of Mg2Gd8(SiO4)6O2:Tb3+ was compared to investigate as a function of Tb3+ ions concentration, which revealed that these nanophosphors showed a strong green emission from 5D4 to 7F5 at 543 nm.
Keywords: Luminescence; Nanophosphors; Coral-like morphology; Doped Tb3+; In situ composition; Hybrid precursors;

The first 1,2,3-tris(phosphinomethyl)ferrocene by Ian R Butler; Peter N Horton; Kevin M Fortune; Kevin Morris; Christopher H Greenwell; Graham R Eastham; Michael B Hursthouse (923-928).
The synthesis of the first 1,2,3-tris(phosphinomethyl)ferrocene is reported using an efficient lithiation and quench technique in which dimethylaminomethylferrocenes are useful intermediates.
Keywords: Ferrocene; Phosphines; Ligand;

A novel and low-temperature hydrothermal synthesis of SnO2 nanorods by Caixin Guo; Minhua Cao; Changwen Hu (929-931).
SnO2 nanorods with the rutile structure have been successfully synthesized by a novel hydrothermal method. This process requires no high temperature. In this reaction, the surfactant cetyltrimethyl ammonium bromide (CTAB) plays an important template-directed role. Select-area electron diffraction (SAED) and X-ray diffraction (XRD) showed that the nanorods were crystalline with the rutile structure. The morphologies of the as-prepared products were characterized by scanning electron microscopy (SEM). The effect of the concentration of SnCl4 on the morphology was discussed.
Keywords: SnO2 nanorods; Hydrothermal synthesis; Template-directed method;

The chelate (N,N -dimethylethylenediamine-[60]-fullerene)copper(II) bromide was synthesized in 79% yield by the dropwise addition of a solution of N,N -dimethylethylenediamine-[60]-fullerene in tetrahydrofuran (THF) to a solution of excess copper(II) bromide in THF. The resulting brown precipitate was characterized by electron spin resonance (ESR) spectroscopy and elemental analysis.
Keywords: Fullerene; N,N -Dimethylethylenediamine; Copper complex; Copper chelate; ESR spectroscopy;