Inorganic Chemistry Communications (v.3, #11)

Novel triosmium clusters derived from the reaction of [Os3(CO)10(μ-dppm)] with 1-vinylimidazole by Jasmin Akter; Kazi A. Azam; Shariff E. Kabir; K.M. Abdul Malik; Md. Abdul Mottalib (553-556).
The reaction of [Os3(CO)10(μ-dppm)] (1) with 1-vinylimidazole at 110°C afforded two novel trosmium compounds, [(μ-H)Os 3 (CO) 7(μ-2,3-η2- C=NCH=CHN CH=CH 2) (η1- CH=NCH=CHN –CH=CH2){μ33-PPhCH2PPh(C6H4)}] (3) and [Os3(CO)8(μ-2,3-η2- C=NCH=CHN CH=CH 2 )(η1- CH=NCH=CHN CH=CH 2 )(μ32-PPhCH2PPh2)] (4). The compounds have been characterized by elemental analysis, IR, 1H and 31P{1H} NMR and mass spectrometry together with an X-ray analysis for 3, which has a unique structure with a bridging hydride, an N-coordinated η1-vinylimidazole, a dimetallated μ-η2-vinylimidazolide and a μ33-PPhCH2PPh(C6H4) ligands.
Keywords: Osmium; Clusters; 1-Vinylimidazole; Crystal structures; Metallation;

This paper describes the synthesis and spectroscopic study of a titanium(IV) silsesquioxane complex, which is heterogenised in the pores of an MCM-41 host material. Its immobilization is performed via chemical bonding, not by means of physical adsorption. As a linking molecule between the MCM-41 carrier and the silsesquioxane, (3-glycidyloxypropyl)trimethoxysilane is used. Characterization is performed by using nitrogen adsorption techniques, TGA, diffuse reflectance infrared spectroscopy (DRIFT) and ICP-MS. Also its catalytic activity towards the epoxidation of alkenes shows interesting results.
Keywords: Titanium; Silsesquioxane; MCM-41; Olefin epoxidation;

Cu2+-cyclam complex functionalised with naphthylmethyl fluorescent signalling subunits as fluorescent chemosensors for sulfate in aqueous environment. by Youseff Al Shihadeh; Angel Benito; José Manuel Lloris; Ramón Martı́nez-Máñez; Juan Soto; M.Dolores Marcos (563-565).
The fluorescent behaviour of the polyazacycloalkane containing naphthyl groups 1,4,8,11-tetrakis(naphthylmethyl)-1,4,8,11-tetraazacyclotetradecane (L1) and its Cu2+ complex in the presence of anions are compared in aqueous environment (THF:water 70:30 v/v, 0.1 mol dm−3 tetrabutylammonium perchlorate, 25°C). The emission fluorescent intensity of the L1–Cu2+ system is selectively enhanced in the presence of sulfate at acid pH.

A dinuclear nickel(II) complex bridged by tricyanomethanide: structure and magnetic properties by Milan Gembický; Roman Boča; Lothar Jäger; Christoph Wagner (566-571).
Complexation of NiII ion with triethylenetetramine (teta) and potassium tricyanomethanide KC(CN)3 yielded a new binuclear complex, [(teta)Ni(C(CN)3)2Ni(teta)](ClO4)2 (1), where two nickel(II) centres are held together by two tricyanomethanide bridges. The dinuclear units are aggregated into ladders; four of them being identified inside the unit cell. The effective magnetic moment on the cooling exhibits a slight gradual increase until 25 K; below this limit a strong, abrupt ferromagnetic interaction culminating at 16 K appears.
Keywords: X-ray structure; Dinuclear nickel(II) complex; Ferromagnetic interaction; Pseudohalide;

Crystal structure of tetrabutylammonium [bis(1,3-dithiole-2-thione-4,5-dithiolato)bismuthate(1-)], [NBu4][Bi(dmit)2] by Nadia Maria Comerlato; William T.A Harrison; R.Alan Howie; Alexandre Carneiro Silvino; James L Wardell; Solange M.S.V Wardell (572-574).
The crystal structure of ionic [NBu4][Bi(dmit)2] (5: Q=NBu4), obtained from BiBr3 and [NBu4]2[Zn(dmit)2], has been determined. The bismuth atoms are six coordinate, as a consequence of two inter-anion Bi–S contacts with two neighbouring anions. In addition to the four intra-anion Bi—S bonds to the two thiolato S atoms of the dmit ligands [Bi–S between 2.5872(14) and 2.8082(13) Å: the inter-anion bonds involve thione S atoms [Bi—S(10)i=3.2548(11) and Bi–S(10)ii 3.4628(13) Å]. Excluding consideration of any lone pair effect, the Bi atoms have very distorted octahedral geometries. The anions form centrosymmetric pairs of chains with the shortest Bi–Bi distance of 4.180 Å being between the pairs of chains; overlapping parallel dmit ligands, within the pairs of chains, are separated by a perpendicular distance of 3.477(2) Å, with the dmit centroid–dmit centroid separation of 3.529 Å, ideal for π–π interaction.
Keywords: Crystal structure; Bismuth complex; Dmit complex; π–π interactions;

The first example of aryl transfer to palladium(II) with concomitant oxidation to palladium(IV) is reported, utilising the reaction of PdMe2(bpy) (bpy=2,2’-bipyridine) with [IPh2][O3SCF3], together with studies of an analogous platinum system and a structural analysis of trans-PtIMe2Ph(bpy) (bpy=2,2’-bipyridine).
Keywords: Organopalladium(IV); Organoplatinum(IV); Iodonium; Exchange reactions;

A novel and large heteropolyanion [(BiW9O33)3Bi6(OH)3(H2O)3V4O10]12− has been synthesized by reaction of sodium metavanadate with Na9[BiW9O33]·16H2O in acetate buffer solutions (at pH 4.8). The present anion has a trilobal structure in which three α-B {BiW9O33} units are connected to each other by an unique core [Bi6(OH)3(H2O)3V4O10]15+. A central bismutate/vanadate-mixed core comprises three sets of two types of the BiO6 pentagonal pyramid, the edge-sharing VO5 square-pyramidal triad, and a VO4 tetrahedron.
Keywords: Crystal structure; Polyoxometalates; Bismutate/vanadate-mixed cluster;

A novel double-stranded dinuclear copper(I) helicate having a photoluminescent CuI 2N8 chromophore by Pankaj K. Pal; Shubhamoy Chowdhury; Pradipta Purkayastha; Derek A. Tocher; Dipankar Datta (585-589).
Bis-(pyridinal)-ethylenediimine (L) affords [CuI 2L2]X2 (X=ClO4 and PF6 ). The X-ray crystal structure of the ClO4 salt shows that the cation [CuI 2L2]2+ is a double-stranded helicate. The PF6 salt exhibits a single emission band (maxima, 540 nm) in solution at room temperature (quantum yield: 2×10−5 in methanol, 1×10−5 in CH2Cl2).
Keywords: Copper(I) complexes; Helicates; Photophysics; Crystal structures;

Theoretical characterisation of the origin of symmetry distortions in TpCuCl complexes by Lourdes Cucurull-Sánchez; Feliu Maseras; Agustı́ Lledós (590-593).
IMOMM(Becke3LYP:MM3) calculations on the [TptBu]CuCl and [TptBu,Me]CuCl complexes show that the non-symmetrical arrangement observed around the Cu(II) centre is essentially controlled by a Jahn–Teller effect, and rather independent of the sterical demands of the particular tris(pyrazolyl)borate ligands.
Keywords: Hybrid calculations; Copper; Pyrazolylborates; Jahn–Teller distortion;

Photoluminescence of tetrameric platinum(II) acetate in solution by Horst Kunkely; Arnd Vogler (594-596).
Tetrameric Pt(II) acetate shows a photoluminescence in solution at λ max=510 nm and 630 nm which is assigned to a metal-centered fluorescence (τ<5 ns) and phosphorescence (τ=1.8 μs), respectively. It is suggested that in the emissive excited state the metal–metal bonds are weakened.
Keywords: Platinum complexes; Luminescence;

The complex with the formula [NiL](ClO4)2, where L=3,10-bis(2-phenylethyl)-1,3,5,8,10,12-hexaazacyclotetradecane, has been synthesized and characterized by single-crystal X-ray analyses. The complexes combine via hydrophobic interaction of lariats to form hydrophobic wall and hydrophilic cavity. All the ClO4 anions are involved in the cavities.
Keywords: Nickel macrocyclic complex; Crystal structure; Hydrophobic wall, hydrophilic cavity;

Investigation of the tetracarbonatozirconate ion by electrospray mass spectrometry in aqueous media by Anne Veyland; Laurent Dupont; Jean-Claude Pierrard; Jean Rimbault; Michel Aplincourt; Ludovic Devoldere (600-607).
Reported here is the study of zirconium (IV) aqueous solutions in carbonate media by electrospray ionisation mass spectrometry (ESI–MS). Spectra analysis lead to consider the existence in the spray of the initial pseudomolecular labile species [Zr(CO3)4(HCO3)]5−, xH+, (6−x) K+ (or Na+). The existence of this species confirms the associative exchange mechanism of carbonate ions with [Zr(CO3)4]4− ion.
Keywords: Mass spectrometry; Electrospray; Fragmentation; Carbonatozirconium complexes;

Detection of complex formation between binuclear iron(III)–peroxide adduct and oligonucleotide by electrospray mass spectrometry by Teruyuki Kobayashi; Satoshi Nishino; Hideki Masuda; Hisahiko Einaga; Yuzo Nishida (608-610).
Electrospray mass spectrometry (ESI–Mass) gave clear evidence for complex formation between an iron(III) complex and a DNA chain, and also between a binuclear iron(III)–peroxide adduct and a DNA chain.
Keywords: Binuclear iron(III)–peroxide adduct; Complex formation between metal; Compound and oligonucleotides; Electrospray mass spectrometry;

Living polymerization of 1-hexene due to an extra donor arm on a novel amine bis(phenolate) titanium catalyst by Edit Y Tshuva; Israel Goldberg; Moshe Kol; Zeev Goldschmidt (611-614).
Two amine bis(phenolate) titanium dibenzyl complexes were synthesized in one-pot reactions starting from the ligand precursors and titanium tetra(isopropoxide). The catalyst derived from a ligand having an extra donor on a side arm leads to living polymerization of 1-hexene at room temperature, whereas the one derived from a ligand lacking it, leads to low molecular weight poly(1-hexene) with PDI values of around 2.0.
Keywords: Phenolate ligands; Titanium complexes; Living polymerization;

Polyoxometalate coordinated phosphato complexes: a possible model reaction for POM-nucleotide interaction by Jun Peng; Wen-zhuo Li; En-bo Wang; Xian-ling Zhao; Bo-Qu Huang (615-616).
The dephosphorylation of ATP in the presence of unsaturated heteropoly anion [SiW11O39]8− and transition metal ions, MnII, CoII, NiII and ZnII, generates phosphato derivatives, formulated as [SiW11O39M(P2O7)] 10−, (M= MnII, CoII, NiII and ZnII), which were also synthesized from pyrophosphate as a possible model reaction of polyoxometalate-nucleotide interaction.
Keywords: Polyoxometalate; Nucleotide; Dephosphorylation; ATP;

The carbonylation of methylacetate to acetic anhydride catalysed by [Cp Rh(CO)2] in the absence of hydrogen by Andrew C. Marr; Philip Lightfoot; Evert J. Ditzel; Andrew D. Poole; Gary P. Schwarz; Douglas F. Foster; David J. Cole-Hamilton (617-619).
[Cp Rh(CO)2] catalyses the carbonylation of methylacetate to acetic anhydride at 6.9 mol dm3  h−1 in the absence of hydrogen; [Cp RhI2(CO)] which forms from it is also catalytically active giving rates of 1.2 mol dm3  h−1 under the same conditions. ▪
Keywords: Methyl acetate; Carbonylation; Acetic anhydride; Rhodium; Pentamethylcyclopentadienyl; WGSR;

Coordination of [RhI(ED)Cl]2 and [RhI(Chel)(ED)]+ complexes (ED=1,5-hexadiene; Chel=2,2'-bipyridine and 4,4'-dimethyl-2,2'-bipyridine) in poly(pyrrole-2,2'-bipyridine) films has been investigated by cyclic voltammetry in CH3CN electrolyte, and by FT-IR. In any case, the formation of stable poly[Rh(Chel)(ED)]+ films contrasts to that observed in the presence of an excess of Chel in acetonitrile, where the reaction of rhodium(I) complexes containing the labile ED ligand leads to [Rh(Chel)2]+ species.
Keywords: Rhodium complexes; Poly(2,2'-bipyridine); 1,5-Hexadiene; Metallopolymer films; Electrochemistry;

The NAD+ subunit 1-methyl-3-carbamoyl pyridinium cation (or 1-methyl nicotinamide cation, MNA+) forms an ion pair with BH3CN which shows a new absorption (λ max=453 nm) which is assigned to an outer-sphere charge transfer (OSCT) transition from BH3CN to MNA+. At r.t. this ion pair is not stable and undergoes a hydride transfer from BH3CN to MNA+ with the formation of MNAH. At −77°C this ion pair is persistent but the hydride transfer occurs as a photoreaction which is induced by OSCT excitation.
Keywords: Charge transfer; Photochemistry; Borohydride;

Cobalt(II) complexes of the form CoX2(NH2CH2CH{OEt}2)2 [X=Cl, Br, I] react hydrolytically in solution to convert hemiacetal moieties to aldehydes, the latter undergoing Schiff base condensation. Complex decomposition and the separation of metal salt and organic material occur concomitantly. In contrast, thermal reactions afford metal complexed polyimines of the form CoX2{=NCH2CH=}2. Analyses are consistent with the liberation of four equivalents of ethanol per mole of CoX2(NH2CH2CH{OEt}2)2 via an autocatalytic cycle of hemiacetal hydrolysis and Schiff base condensation. Such thermal routes offer facile access to metal complexed polyimines.
Keywords: Cobalt(II); Amine; Acetaldehyde; Polymerization; Schiff base;

The symmetrical, bipodal ligand N′,N′,N′′′,N′′′-tetraethyl-N,N′′-pyridine-2,6-dicarbonyl-bis(thiourea) (tepytu) and silver(I) perchlorate yield a coordination polymer {[Ag2(tepytu)3](ClO4)2} n . The compound was characterized by electrospray mass spectrometry, as well as IR, 1 H and 13 C NMR spectroscopy. The structure of the coordination polymer has been determined by X-ray diffraction analysis. The tepytu ligands act as bidentate S,S-donors towards silver. Two silver ions and two tepytu molecules form a cyclic subunit, whereas the third tepytu of the formula unit links to the next [Ag(tepytu)2]-subunit by coordinating each of its thiocarbonyl sulfur atoms bridging towards both silver ions of one subunit. This results in an infinite one-dimensional chain leaving each silver ion coordinated in a highly distorted tetrahedral fashion.
Keywords: Coordination polymer; One-dimensional chain; Silver; Thiourea ligand;

Photocatalytic decomposition of trichlorophenol by zinc(II) phthalocyanine derivatives in aerated organic solvents by Kuninobu Kasuga; Atsushi Fujita; Takahiro Miyazako; Makoto Handa; Tamotsu Sugimori (634-636).
Trichlorophenol was photodecomposed by irradiation with visible light using zinc(II) phthalocyanine derivatives as a photosensitizer in aerated organic solvents. An oxidative quenching pathway via a generation of hyperoxide was proposed.
Keywords: Phthalocyanine; Trichlorophenol; Photosensitizer; Hyperoxide;

New uranyl nitrate complex with N-cyclohexyl-2-pyrrolidone: a promising candidate for nuclear fuel reprocessing by T.R Varga; M Sato; Zs Fazekas; M Harada; Y Ikeda; H Tomiyasu (637-639).
Bis(N-cyclohexyl-2-pyrrolidone) uranyl nitrate complex was prepared from uranyl nitrate and N-cyclohexyl-2-pyrrolidone (NCP) in 7 M aqueous nitric acid solution with a yield of 68%. The yellow UO2(NO3)2(NCP)2 complex was precipitated from this highly acidic media and was characterized by NMR, IR and UV-vis spectroscopies.
Keywords: N-cyclohexyl-2-pyrrolidone; Uranyl nitrate; Complex; Nuclear fuel reprocessing;

Cationic [RuIII(app)(pic)(H2O)]+ (1) complex (Happ=N-(hydroxyphenyl)pyridine-2-carboxaldimine; Hpic=picolinic acid) has been synthesized and characterized by physico-chemical methods and employed as catalyst in the oxidation of both saturated and unsaturated hydrocarbons using tert-butylhydroperoxide (t-BuOOH). A mechanism involving formation of and transfer from a reactive high valent Ru(V)-oxo species as catalytic intermediate is proposed for the catalytic processes.
Keywords: Oxo transfer catalysis; Ruthenium complex; t-BuOOH; Cyclohexene; Cyclohexane;

Photoluminescence of 8-quinolinolato(trioxo)rhenium(VII) by Horst Kunkely; Arnd Vogler (645-647).
The complex ReVIIO3(oxinate) (oxine=8-quinolinol or 8-hydroxyquinoline) shows a green fluorescence at λ max=511 nm with φ=0.012 and a very weak red phosphorescence at λ max=645 nm. Both emissions originate from the lowest-energy ππ* intraligand state of the oxinate ligand. Owing to the d0 electron configuration and the high oxidation state of rhenium the heavy atom effect transmitted to the π-electron system of the oxinate ligand is very weak.
Keywords: Rhenium complexes; Luminescence;

A preconstrained tricyclic biimidazoline ligand adaptable to diverse coordination modes by Daniel W Widlicka; Edward H Wong; Gary R Weisman; Kim-Chung Lam; Roger D Sommer; Christopher D Incarvito; Arnold L Rheingold (648-652).
The tricyclic biimidazoline ligand L possesses a preconstrained synperiplanar bisamidine N=C–C=N and has been shown to have a versatile coordination chemistry. In its manganese(II) tris-chelate complex [MnL 3](ClO4)2, a distorted trigonal prismatic coordination geometry is adopted. By contrast, a square–planar copper(II) complex, [CuL 3](ClO4)2 features one chelating as well as two monodentate L’s. In a third variation, an exclusively α-diimine-bridged dicopper unit is found in both the copper(I) [Cu2 L 3](BF4)2 and copper(II) [Cu2 L 4](ClO4)4 dimeric complexes.
Keywords: Biimidazoline ligand; Dicopper complexes; Bridging mode; Manganese(II) complex;

Using betaine ((CH3)3N+CH3CO2 )) as the zwitterionic ligand, a novel cyano-bridged complex [Gd(bet)2(H2O)3Fe(CN)6] n (bet=betaine) has been synthesized, which possess one-dimensional chain structure through two approximately parallel cyano-bridges between Gd and Fe atoms and the CN···HO hydrogen bonding. The complex crystallizes in the orthorhombic, space group P212121, cell dimensions a=9.459(2) Å, b=14.569(3) Å, c=17.751(4) Å, V=2446.2(9) Å3, Z=4, D c=1.791 Mg/m3, F(000)=1312, GOF=1.043, R 1=0.0264. There exist weak antiferromagnetic interaction between the Gd and Fe atoms.
Keywords: Cyano-bridged complex; One-dimensional chain; Crystal structure; Betaine;

The first copper(I) silsesquioxane derivative, Cu4O4[Cy7Si7O9(OSiMe3)]2 (4) was prepared by reacting tetrameric copper(I)-t-butoxide, (CuOtBu)4 (3), with the monosilylated silsesquioxane precursor Cy7Si7O9(OH)2(OSiMe3) (2) in a 1:2 molar ratio. An X-ray diffraction study revealed the presence of a centrosymmetric dimer. A slightly puckered Cu4O4 ring forms the central part of a complex structure comprising nine eight-membered inorganic ring systems.

A heptanuclear Fe(II)–Fe(III)6 system with twelve unpaired electrons by Milan Gembický; Roman Boča; Franz Renz (662-665).
The pentadentate ligand 5 LH2 = saldptn = N,N′-bis(1-hydroxy-2-benzyliden)-1,7-diamino-4-azaheptane has been prepared by a Schiff base condensation between 1,7-diamino-4-azaheptane and the corresponding salicyaldehyde. Its complexation with Fe(III) gave the high-spin (S=5/2) complex of [Fe III (5 L)Cl]. This precursor was combined with [Fe(CN)6]4− and a blue heptanuclear complex [FeII{(CN)Fe III (5 L)}6]Cl2 resulted. This system belongs to the class of high-spin molecules possessing twelve unpaired electrons (S=6) as proven by the magnetic susceptibility measurements and Mössbauer spectra.
Keywords: Heptanuclear iron complex; High-spin molecule; Iron(II)–iron(III) mixed valence; Magnetic susceptibility; Mössbauer spectra;

Synthesis, structure and optical characteristics of pyridyl substituted diketonates of lanthanoids by Stefan Brück; Matthias Hilder; Peter C Junk; Ulrich H Kynast (666-670).
Lanthanoid complexes of a dipyridylsubstituted β-diketonate ligand have been prepared and their structure and optical characteristics have been explored. The structure of these complexes are ten-coordinate centrosymmetric dimers with quadruply bridging diketonate ligands, terminal diketonate ligands and ‘dangling' and bound pyridyl nitrogen atoms. The europium complex diplays strongly luminescent properties while the terbium analogue is completely quenched.
Keywords: Lanthanoid; Luminescence; B-diketones; X-ray structure;

Effect of organic solvents on the thermal stability of porous silica-modified alumina powders prepared via one pot solvothermal synthesis by Piyasan Praserthdam; Masashi Inoue; Okorn Mekasuvandumrong; Waraporn Thanakulrangsan; Suphot Phatanasri (671-676).
Mixture of aluminum isopropoxide (AIP) and tetraethyl orthosilicate (TEOS) with weight ratios of AIP/TEOS=8 in various organic solvents was set in an autoclave and heated at 300 oC for 2 h. The fluid phase was removed at the supercritical temperature. The products were calcined in air to yield silica-modified aluminas. These silica-modified aluminas had different morphology that affected the surface area and thermal stabilities at high temperatures. The reactions of AIP and TEOS in 1-butanol gave substantially the wrinkled sheets morphology having the higher thermal stability than the spherical particles obtained by reaction in toluene.
Keywords: Supercritical; Wrinkled sheet; Spinel; Silica-modified alumina;

TDDFT study of electronic spectra of photochromic dinuclear molybdenum complex by Kan Wakamatsu; Kichisuke Nishimoto; Takashi Shibahara (677-679).
The time-dependent density functional theory (TDDFT) was applied to the calculation of the electronic spectrum of a dinuclear molybdenum complex, [Mo2(μ-S2)(μ-S2C2R2)2 (S2C2R2)2] (R=H), which was a model for the photochromic complex (R=Ph). The calculated results showed that TDDFT based on B3LYP theory would be useful for the calculation of electronic spectra of molybdenum compounds.
Keywords: Time-dependent density functional theory; Dinuclear molybdenum complex; Photochromism; Excitation energy;