Inorganic Chemistry Communications (v.5, #10)

Contents List (iii-v).

Preparation and characterization of MnOOH and β-MnO2 whiskers by Xiaodan Sun; Chunlai Ma; Yude Wang; Hengde Li (747-750).
MnOOH and β-MnO2 whiskers are obtained for the first time in our work. MnOOH whiskers are chemically synthesized in the presence of cationic surfactant cetyltrimethylammonium bromide (CTAB). The product is obtained under extremely low surfactant concentrations under basic conditions, using MnSO4·H2O as the manganese source and ethylamine as the alkali source. After the subsequent heat treatment of MnOOH at 300 °C for 1 h, β-MnO2 whiskers retaining the similar morphologies are obtained. Powder X-ray diffraction (XRD), transmission electron microscopy (TEM), scanning electron microscopy (SEM) and thermogravimetry analysis (TGA) are used to characterize the products.
Keywords: Manganese oxides; Whisker; Surfactant; Chemical Synthesis;

Preparation of nanocrystalline metal oxide powders with the surfactant-mediated method by Yu-de Wang; Chun-lai Ma; Xiao-dan Sun; Heng-de Li (751-755).
Nanocrystalline metal oxides (ZnO, NiO, and SnO2) powders with an average particle diameter of 18–55 nm have been successfully prepared with the surfactant-mediated method. The cationic surfactant (cetyltrimethylammonium bromide, CTAB) and the hydrous metal chlorides (ZnCl2·2H2O, NiCl2·6H2O, and SnCl4·5H2O) appear to be the good candidates for obtaining a high yield of nanoparticles. The resultant products have been characterized by thermogravimetric analysis (TGA), X-ray powder diffraction (XRD), and transmission electron microscopy (TEM). The resulting powders are highly crystalline and largely monodisperse oxide particles. The surfactant-mediated method turned out to be suited for the preparation of the nanocrystalline oxide powders. Through this method, it is possible to obtain nanocrystalline metal oxide powders.
Keywords: Nanocrystalline powder; Surfactant-mediated method; Metal oxides; Monodisperse;

A polymeric compound, [Cu(S-metamp)(H2O)(NO3)] (1) [S-metamp (=4(S)-1-(2-pyridyl)-3-oxo-4-aza-7-thiaoctane)] was prepared and characterized by X-ray crystallography. Crystal data for 1 monoclinic, P21, a=7.7799(7) Å, b=20.613(2) Å, c=9.815(1) Å, β=90.287(8), V=1573.9(3) A ̊ 3 , Z=4 and R=0.0306. In 1, the coordination geometry around Cu(II) ion is distorted square-pyramidal with an oxygen atom from nitrate at the apex, and three nitrogen atoms from S-metamp and an oxygen from aqua ligand in a plane. The two hydrogen atoms of the coordinated water molecule interact with the oxygen atom of nitrate and amide oxygen atom by hydrogen bonding in the solid state. The combination of this gives a structural feature in a 2D polymeric arrangement.
Keywords: Cu(II) complex; Organic amide; Chiral ligand; Hydrogen bonding;

A porous coordination polymer, Co3(citrate)2(4,4-bipyridine)4(H2O)2·4(H2O) has been synthesized and characterized. It adopts a 3-D framework, built up by parallel [Co3(citrate)2] n chains cross-linked by 4,4-bipyridine ligands. The connection leads to hydrophilic cavities filled with water molecules, which interact with the citrate ligands through hydrogen bonds. Dangling 4,4-bipyridine ligands are observed in the structure, pointing to cavities. Two equivalents of coordination water and four equivalents of crystallization water molecules can be removed reversibly based on TGA studies.
Keywords: Porous; Coordination polymer; Citrate; Hydrophilic cavities;

Novel approach to boron-10 enriched decaborane(14): an important advance in synthetic boron hydride chemistry by Luqman Adams; Susan Tomlinson; Jianhui Wang; Sumathy N. Hosmane; John A. Maguire; Narayan S. Hosmane (765-767).
The oxidative polyhedral cage-fusion reaction of the sodium or lithium salt of the B-10 enriched pentaborate anion, [10 B 5 H 8] , with anhydrous FeCl3, NiCl2, Br2, or C5H11Br, followed by room temperature sublimation of the product, produced 10 B 10 H 14 (3) in 52–65% yields.
Keywords: Boron-10 enriched; Pentaborane(9); Decaborane(14); Anti-B18H22, Synthesis, BNCT; Boron hydrides; 10B-NMR;

Molecular assembly of novel hetero-metal clusters: [(O=MoS3Cu2)2(μ-Sn2S6)]4− and [(S=MoS3Cu2)33-S)2]4− by Wenjian Zhang; Xintao Wu; Martin Ebel; Dongren Wang; Dieter Rehder (768-770).
Two mixed molybdenum–copper–sulfur clusters containing two or three {E=MoS3Cu2} (E=O, S) fragments have been assembled around the nucleophiles μ2-Sn2S6 4− or μ3-S2−, viz. [(MoES3Cu2)2(μ-Sn2S6)]4− (E=0.7 O + 0.3 S) and [(MoS4Cu2)33-S)2]4−.Nucleophilic butterfly type fragments {E=Mo(μ-S)3Cu2} (E=O, S) have been linked by the electrophiles Sn2S6 4− or S2− to yield novel di- and trimolybdenum clusters.
Keywords: Molybdenum–sulfur clusters; Copper–sulfur clusters; Hexathiodistannate;

Two novel complexes with the composition {[Ni( L )]·(btc 2−)}n (1) {L=3,10-bis(2-hydroxyethyl)-1,3,5,8,10,12-hexaazacyclotetradecane; btc2−=1,2,4,5-benzenetetracarboxylic acid dianion} and [Ni( L )]·(btc 2−)·(btc) (2) were obtained from the reaction between [Ni( L )Cl 2] and btc (btc=1,2,4,5-benzenetetracarboxylic acid), and their structures were determined by analytical, spectroscopic, and X-ray diffraction methods. The orange complex 1 contains a 1D hydrogen bonded polymeric chain with nickel(II) macrocycles and bridging btc2− ligands. The nickel(II) coordination geometry in 1 is best described as a square-plane with four Ni–N bonds. The weak interactions between the nickel(II) ions and the oxygen atoms of the btc2− ligand are also found. The yellow complex 2 has a monomeric structure which is composed of a nickel(II) macrocycle, a counter anion btc2−, and a free acid btc (btc=1,2,4,5-benzenetetracarboxylic acid). The nickel(II) coordination geometry in 2 is square-planar, where the tetra-valent nickel(II) ion is completed with four nitrogen atoms from the macrocycle. In addition to the presence of counter anion btc2−, the free acid btc is also found in 2, which participates in abundant hydrogen-bonding interactions.
Keywords: Crystal structure; Nickel complex; Macrocyclic ligand complex; Benzenetetracarboxylic acid;

The copper complex [Cu(HL)](ClO4)2·2H2O, where HL is N-[2-(4,7-dimethyl-1,4,7-triazacyclonon-1-yl)ethyl]–N-(benzimidazol-2-yl)methanimine, has been prepared and characterised by X-ray crystallography and solution absorption spectroscopy. Deprotonation of the benzimidazole moiety in this complex has been investigated by electronic spectroscopy. The results show a definite shift in λ max for [Cu(HL)]2+, at 632–818 nm for the deprotonated [CuL]+, in acetonitrile. This complex has been synthesised as a structural homologue to half of the enzyme Cu–Zn superoxide dismutase (SOD) which contains a bridged imidazolate moiety between the two Cu and Zn metal ions.
Keywords: Biomimetic complex; Functionalised triazacyclononane; Superoxide dismutase;

The bis(phosphine), Ph2POCH2CH2N(CH3)PPh2 (1) reacts with [Pt(COD)Cl2] to give seven-membered cis-chelated complex 2. The complex was characterized by elemental analysis, IR, and NMR spectroscopic methods of which the 31 P{1 H} NMR data is very informative and allows the direct measure of the P–P coupling through metal centers otherwise can not be seen in the free ligand as the two phosphorus centers are five-bonds apart. The structure of the platinum(II) complex was determined by X-ray crystallography.
Keywords: Unsymmetrical bis(phosphine); Platinum complex; Through-metal coupling; Chelate;

Reaction of 2,6-bis(pyrrolidin-2-yl)pyridine (LH4) with RuCl3·3H2O in refluxing methanol/water mixtures gives rise to the formation of the octahedral complexes [Ru(LH4)(L)]2+, in which one of the two trihapto ligands has been dehydrogenated as 2,6-bis(3,4-dihydro-2H-pyrrol-5-yl)pyridine (L), even if LH4 was present in excess. With the three stereoisomers of LH4, the complexes [Ru(R,S-LH4)(L)]2+ (meso), [Ru(R,R-LH4)(L)]2+ and [Ru(S,S-LH4)(L)]2+ have been isolated as the perchlorate salts and characterised by X-ray structure analysis and by CD spectra.
Keywords: Crystal structures; Ruthenium(II) complexes; Amine dehydrogenation; Chirality; Octahedral geometry; Tridentate ligand;

The neutral three-dimensional cyano-bridged bimetallic coordination polymer, {[Cu(en)2][Cu(en)][Mo(CN)8]} n ·4nH2O (en=ethylenediamine), has been synthesized and characterized. X-ray study shows that the asymmetric unit of the three-dimensional Cu(II)–Mo(IV) polymeric assembly consists of two half [Cu(en)2]2+ cations, a [Cu(en)]2+ cation and a [Mo(CN)8]4− ion, together with four water molecules. The latter Cu site is coordinated by two N atoms from an en ligand and by three cyanides in a distorted square-pyramidal environment. The Cu(II) ions of the two [Cu(en)2]2+ cations on the centers of inversion reside in an elongated octahedral geometry, and one of the [Cu(en)2]2+ cations is encapsulated in a ‘box’ formed by two pairs of co-lateral Cu2Mo2(CN)4 12-membered macrocyclic units. The Mo(VI) atom is coordinated by eight cyanides in an irregular square antiprism. Five of these acting as bridging units connect the Mo and the three Cu atoms to form an infinite three-dimensional porous network containing a zigzag-ladder structure.
Keywords: Crystal structure; Coordination polymer; Porous network; Zigzag-ladder structure;

Synthesis and crystal structure of the dimeric, Ti–O–Ti bridged hydrid form polyoxoanion [α-1,2-PW10Ti2O39]2 10− by Jianghua He; Xiaohong Wang; Yaguang Chen; Jingfu Liu; Ninghai Hu; Hengqing Jia (796-799).
The reaction of trivacant precursor Na9[A–PW9O34]·19H2O with Ti(SO4)2 affords the novel dimeric, di-TiIV-substituted tungstophosphate K4Na6[α-1,2-PW10Ti2O39]2·14H2O. The X-ray structural determination shows the dimeric, anhydride structure was formed by two Ti–O–Ti bonds linking two di-titanium-substituted Keggin anion [α-1,2-PW10Ti2O40]. It was also characterized by elemental analysis, TGA, FT-IR and UV–vis spectroscopies.
Keywords: Titanium-substituted polyoxometalates; Dimeric tungstophosphate; Crystal structure; K4Na6[α-1,2-PW10Ti2O39]2·14H2O;

Inter-ligand interactions and the selective formation of the unusual metal–N3(adenine) bond in ternary copper(II) complexes with N-benzyliminodiacetato(2−) ligands by M.J. Sánchez-Moreno; D. Choquesillo-Lazarte; J.M. González-Pérez; R. Carballo; A. Castiñeiras; J. Niclós-Gutiérrez (800-802).
A novel mixed-ligand copper(II) complex with N-(p-methoxybenzyl)-iminodiacetato(2−) ligand (MOBIDA) and adenine (AdeH) of formula [Cu(MOBIDA)(AdeH)(H2O)]·H2O has been obtained. Its crystal structure reveals the selective formation of a rare Cu–N3(AdeH) bond, closely related to those reported by first time for compounds of general formula [Cu(B)(AdeH)(H2O)]·H2O, with B=N-benzyl- or N-(p-methylbenzyl)-iminodiacetato(2−) ligands. Appropriate structural comparison reveals that the copper(II) coordination by less basic N3 heterocyclic donor of the nucleobase is controlled by a molecular recognition process involving the formation of an intra-molecular inter-ligand N7(imidazole-like)–H⋯O(carboxyl) bond and the inter-molecular inter-ligand π,π-stacking interaction between six membered rings of benzyl (MOBIDA) and AdeH. This stack generates multi-stacked infinite chains along the b-axis of the crystal.A new Cu(II) complex with N-(p-methoxybenzy)liminodiacetato(2−) and adenine (AdeH) ligands confirms the selective formation of the Cu–N3(AdeH) bond reinformed by an intra-molecular inter-ligand N9–H⋯O(carboxyl) bond as well as alternating benzyl-AdeH inter-molecular π,π-interactions in multi-stacked chains.
Keywords: Crystal structure; Adenine; N-(p-methoxybenzyl)-imimodiacetate; Copper(II); Aromatic ring–ring π,π-stacking; Molecular recognition;

First example of a Rh–N–C–O–P heterocycle – a rare example of a five membered true heterocycle by Phillip Cheshire; Alexandra M.Z. Slawin; J.Derek Woollins (803-804).
A novel ligand containing an N–C–O–P backbone has been prepared and used to form a rare example of a ‘true heterocycle’ containing a Rh–N–C–O–P ring.The new ligand py–O–PPh2 can behave as a P monodentate or P, N chelate to give easy entry into hemilabile systems which are ‘true heterocycles’.
Keywords: True heterocycle; Co-ordination chemistry; Rhodium complex;

The complexes [M(1,3-bis(N-imidazoyl)propyl-1,1,3,3-tetramethyldisiloxane)2(NCS)2] (M = Mn, Ni) are shown by X-ray studies to form monomers containing 16-membered chelate rings, but replacement of the imidazole donor groups by simple amino groups results in the formation of chains of 24-membered rings in [Ni(1,3-bis(3-aminopropyl)-1,1,3,3-tetramethyldisiloxane)2(NCS)2].
Keywords: Crystal structures; Siloxanes; Polymeric complexes; Large-ring chelates;

Reaction of Ru3(CO)12 with supermesityldiphosphene: a new type of reaction of a Group 8 transition metal carbonyl with a diphosphene by Matthias Freytag; Paul J Dyson; Ludger Ernst; Peter G Jones; Reinhard Schmutzler (808-810).
The reaction of (E)-bis(2,4,6-tri-tert-butylphenyl)diphosphene with Ru3(CO)12 results in cleavage of the P=P bond with concomitant C―H activation of one of the t-butyl groups to form Ru 3(μ-H)2(CO)8(μ-P-C 6 H 2 -2,4- t Bu 2 -6-CMe 2 CH 2)2 . The H-atoms have transferred from the ligand to the metal core.
Keywords: Diphosphine; Transition metal carbonyl cluster; Ruthenium; C―H bond activation;

A new global analysis of EPR, 17O NMR relaxation and chemical shift and 1H NMRD profiles with physically meaningful parameters for [Gd(DOTA)(H2O)] and for [Gd(DTPA)(H2O)]2− in aqueous solution is presented (DOTA=1,4,7,10-tetraaza-1,4,7,10-tetrakis(carboxymethyl)-cyclododecane; DTPA=diethylenetriamine-N,N,N ,N″,N″-pentaacetic acid). The recent developments of an improved EPR relaxation theory, the inclusion of the internal motion of the bound water molecule are the principal modifications. Furthermore the better knowledge of the quadrupolar coupling constant of the bound water molecule, the neglect of the outer-sphere contribution to the chemical shift and the consideration of different isomers for the DOTA complex allowed for an improved analysis. The water exchange and parameters of rotational motion are only slightly changed. Comparison of the contributions of static zero-field-splitting shows that a more symmetric environment of the Gd(III) ion should lead to slower electron spin relaxation, a feature which can become important if all other parameters (rotational correlation time and water exchange rate) are optimised. In the actual stage the improved combined analysis of Gd(III) poly(amino carboxylate) is limited by the approximations of Redfield’s relaxation theory, i.e., very low frequency NMRD-data and slowly tumbling complexes cannot be analysed with the method presented.
Keywords: MRI contrast agents; Simultaneous analysis; Water internal motion; Electronic relaxation; Gadolinium;

The NMR (1H, 13C, 15N and 107Ag) studies of the silver(I) cyanide (AgCN) complexes of thiourea (Tu), N,N -dimethylthiourea (Dmtu) and tetramethylthiourea (Tmtu) were carried out in dimethyl sulfoxide. An upfield shift in 13C NMR and downfield shifts in 1H, 15N and 107Ag NMR are consistent with the sulfur coordination to silver(I). The NMR data shows that C = S–AgCN complexes are stable in solution and do not undergo disproportionation reactions.
Keywords: Silver(I) complexes; Silver cyanide; thioureas; NMR;

Assembly of a tennis ball-like supramolecule coordinatively encapsulating disilver by Il Yoon; Yoon Hee Lee; Jong Hwa Jung; Ki-Min Park; Jineun Kim; Shim Sung Lee (820-823).
Synthesis of the one-to-one dimeric silver(I) complexes (2 and 3), [Ag 2( 1 )2]X 2 (2: X=PF 6 ,  3 : X=ClO4 ), of 1,13-bis(8-quinolyl)-1,4,7,10,13-pentaoxatridecane (1) is described. The crystal structures of the complexes reveal that a couple of the acyclic ligand 1 is reorganized cooperatively by intermolecular π–π stacking, Ag–Ag contacts and coordination. Thus, in both complexes two molecular chains of 1 wrap itself around the two silver atoms, so forming discrete self-complementary tennis ball-like dimers.
Keywords: Podand; Disilver complex; X-ray structure; Supramolecule;

Hydrothermal synthesis and structural characterization of framework microporous mixed tin–zirconium silicates with the structure of umbite by Pilar Pertierra; Miguel A. Salvadó; Santiago Garcı́a-Granda; Anatoly I. Bortun; Sergei A. Khainakov; José R. Garcı́a (824-828).
A novel framework mixed tin–zirconium silicate, K2Sn0.25Zr0.75Si3O9·H2O (1), was synthesized under mild hydrothermal conditions. The unit cell is orthorhombic, a=10.260(2) Å, b=13.272(2) Å, c=7.174(1) Å, space group P212121, Z=4. Isotypic with the mineral umbite, the structural formula may be written as K 2(Sn,Zr){uB,1∞ 1}[3 Si 3 O 9]. In a topotactical process, the K+ ions in compound 1 were replaced by Na+ ions, thus obtaining compound 2: Na2Sn0.25Zr0.75Si3O9·H2O (2), a=10.500(1) Å, b=13.354(2) Å, c=7.2731(9) Å.
Keywords: Silicates; Microporous materials; Hydrothermal synthesis; Crystal structure;

The crystal structures of three new coordination compounds have been determined by X-ray diffraction: reaction of the enantiomerically pure ligands R-1-(4-methoxyphenyl)ethylamine and S-1-(4-chlorophenyl)ethylamine with [Co(Hdmg)2(NO2)(H2O)] (Hdmg = dimethylglyoximate) results in a pair of quasi-racemic complexes. Despite their different molecular conformations in the solid state these compounds can be cocrystallized to give a well-ordered binary solid of superior packing efficiency in which the components are arranged in a pseudo-inversion symmetric fashion.
Keywords: Binary crystals; Quasi-racemates; Cobalt complexes; Pseudo-symmetry; Space filling; X-ray diffraction;

The effect of substitution of a thioether donor by a phosphine donor in thiacrown complexes of iron by Frank E. Sowrey; Philip J. Blower; John C. Jeffery; Elizabeth J. MacLean; Michael J. Went (832-836).
Electrospray mass spectrometry and thermogravimetric analysis reveals that bis(1-phenyl-1-phospha-4,7-dithiacyclononane)iron(II) is more susceptible to ethene loss than bis(1,4,7-trithiacyclononane)iron(II). This is in accord with X-ray crystallographic studies, which show that the C–S bonds are longer in the former complex suggesting an increased population of the C–S σ* π-acceptor orbitals.
Keywords: Bond cleavage; Thioether; Phosphine; Iron complexes; Macrocycle;

The synthesis of the tetrahydroborate complex [(2-iPr2PC6H47-C7H6)Mo(η2-BH4)(P–Mo)] 3 containing the linked cycloheptatrienyl-phosphane ligand [2-(diisopropylphosphanyl)phenyl]cycloheptatrienyl is described, which provides the possibility to generate the 14-electron complex [(2-iPr2PC6H47-C7H6)Mo(P–Mo)]+ (4) on treatment with dimethylanilinium salts such as [HNMe2Ph][BPh4]. Generation of (4)BPh4 in the presence of 2,6-dimethylphenyl isocyanide, 2,5-norbornadiene or phenylacetylene affords the diisocyanide complex (5a)BPh4, the diolefin complex (5b)BPh4 and the alkyne complex (6)BPh4, respectively. The latter complex can be used for the catalytic oligomerization of phenylacetylene affording predominantly the cyclotrimers 1,3,5- and 1,2,4-triphenylbenzene.
Keywords: Cycloheptatrienyl complexes; Molybdenum; Alkyne ligands; Homogeneous catalysis;

First proton-induced near-infrared fluorescent switch at room temperature of a novel Ru(II) complex by Ke-Zhi Wang; Li-Hua Gao; Guang-Yao Bai; Lin-Pei Jin (841-843).
A novel Ru(II) complex, Ru(bpy)2(L)(ClO4)2 (bpy=2,2-bipyridine and L=2-pyridin-2-yl-1H -phenanthro[9,10-d]imidazole) acts as a pH-induced “off/on” near-infrared luminescent switch through protonation and deprotonation in aqueous solution at room temperature.
Keywords: Ruthenium complex; Near-infrared luminescence; Switch;

The novel lanthanide(III) complexes [La(NO3)3(H2O)L] 1, and [Ln(NO3)3L] (Ln=Pr 2, Sm 3, Gd 4) where L=N,N -bis(pyridin-2-ylmethylene)benzene-1,2-diamine, have been obtained by direct reaction of the Schiff base ligand and the corresponding hydrated lanthanide(III) nitrates in methanol. All complexes were characterized spectroscopically and thermogravimetrically. Complex 3 was also characterized with crystallographic studies. In the molecular structure of 3, Sm(III) is surrounded by all four nitrogen atoms of the Schiff base and six oxygen atoms belonging to three bidentate chelating nitrato ligands.
Keywords: Crystal structure; Lanthanide complexes; Schiff bases; 10-coordinate; MRI contrast reagents;

The NHR2/CO2 system as a metal ion extraction reagent from aqueous solution into hydrocarbons: copper(II) and zinc(II) by Daniela Belli Dell'Amico; Fausto Calderazzo; Saverio Farnocchi; Luca Labella; Fabio Marchetti (848-852).
A substantially quantitative transfer of copper(II) or zinc(II) salts from aqueous solution into a hydrocarbon (heptane or toluene) promptly occurs under carbon dioxide in the presence of a dialkylamine (NHR2, R = Bu, Bz). Recovery of the metal complexes from the organic phase affords copper dialkylcarbamates of the formula Cu(O2CNR2)2(NHR2)2 or μ-oxo tetranuclear zinc carbamato complexes, Zn44-O)(O2CNR2)6, respectively, in high yield and purity. An X-ray diffraction study on a single crystal of Cu(O2CNBz2)2(NHBz2)2 1 has shown the compound to be mononuclear with tetracoordinated copper in an almost perfect square-planar geometry. The zinc derivative has the well-established oxo-centred tetranuclear structure (R = Bu, 2).
Keywords: Zinc complexes; Copper complexes; Carbamato complexes; Extraction;

The electrochemistry of [CuL1] 1 and [CuL2] 2 [H2L1=1,2-bis(pyridine-2-carboxamido)benzene, H2L2=3,4-bis(pyridine-2-carboxamido)toluene] was investigated. Both complexes show a quasi-reversible Cu(II/I) reduction near −1.6 V vs Fc+/Fc. Spectroelectrochemistry confirmed that the Cu(III) state is accessible near +0.4 V, and undergoes an EC reaction (k≃10  s −1) to generate a new Cu(II) species.
Keywords: Copper(II)/(III)/(I); Tetradentate ligands; Mononuclear; Electrochemistry; EC reaction;

Two types of polymeric copper(II) complexes, [Cu(trifac)2(4-tfmpda)]2 (1), and [Cu2(hfa)4(4-tfmpda)] (2) were obtained from the reaction of bis(fluorinated-acetylacetonato)copper(II) complexes with 4-(trifluoromethyl)-1,2-phenylenediamine[4-tfmpda] in methylene chloride. 1 crystallizes in the monoclinic space group P2(1)/c, with a=7.840(2) Å, b=11.659(3) Å, c=22.843(6) Å, V=2075.1(9)  A ̊ 3 , and Z=2 with R=0.0474. 2 crystallizes in the triclinic space group P 1 ̄ , with a=11.644(3) Å, b=12.599(4) Å, c=15.171(4) Å, V=1924.5(10)  A ̊ 3 , and Z=2 with R=0.0686. 1 exists as a 1-D infinite polymeric chain where 4-tfmpda is linked by weak coordination bonds around two copper(II) centers, while 2 is a 1-D polymer formed by hydrogen bonds and very weak Cu⋯Cu interactions.
Keywords: Cu(II) complexes; Hydrogen bonds; Coordination polymer; Fluorinated ligand;

A convenient one-step synthesis of alkenyl-phosphonio complexes of ruthenium(II), rhodium(III) and iridium(III) by Yasuhiro Yamamoto; Kenichi Ogata; Katsuaki Kuge; Kazuyuki Tatsumi (862-864).
Alkenyl-phosphonio complexes of ruthenium(II), rhodium(III) and iridium(III) were prepared by reactions of [(p-cymene)RuCl2(PPh3)] or [Cp *MCl2(PPh3)] (M=Rh, Ir; Cp *=C5Me5) with 1-ethynylbenzene and triphenylphosphine in the presence of KPF6.
Keywords: Alkenyl-phosphonio complexes; Ruthenium; Rhodium; Iridium; Pentamethylcyclopentadienyl complexes;

The unique decamolybdodivanadate compound [H3O+]2Na6[MoVI 10VIV 2O38]·7H2O, showing some interesting structural features, was synthesized in high yield by reaction Na2MoO4·2H2O with VOSO 4 in CH3COOH aqueous solution. The title heteropoly compound crystallizes in monoclinic space group Cm with a=14.4522(3) Å, b=14.5042(4) Å, c=10.72530(10) Å, β=113.5960(10)°, V=2060.24(7) Å3, Z=2 and D calc=3.178 g cm−3. The final anisptropic refinement on all metals and partial O atoms gave rise to convergence with R 1=0.0591, wR 2=0.1652 (I>2σ(I)) and GOF=1.065.
Keywords: Heteropoly compound; Decamolybdodivanadate; Synthesis; Crystal structure;

Photoinduced conductivity and nonlinear optical properties of [M(R,Rtimdt)2] dithiolenes (M=Ni, Pd, Pt; R,Rtimdt=monoreduced imidazolidine-2,4,5-trithione) as materials for optically driven switches and photodetectors by M.Carla Aragoni; Massimiliano Arca; Tiziana Cassano; Carla Denotti; Francesco A. Devillanova; Francesco Isaia; Vito Lippolis; Dario Natali; Luigi Nitti; Marco Sampietro; Raffaele Tommasi; Gaetano Verani (869-872).
The unusual NIR-photoconducting properties of [M(Et,Pent-timdt)2] neutral dithiolenes (M=Ni, Pd, Pt; Et,Pent-timdt=monoreduced N-ethyl,N -pentylimidazolidine-2,4,5-trithione) have been investigated with the aim of developing wavelength-selective air-stable photodetectors. In addition, the ps time-resolved dynamics of the absorption saturation has been studied on the Pd-complex by means of pump–probe experiments.
Keywords: Ni, Pd, and Pt dithiolenes; NIR; Photoconductivity; Optoelectronics; I.R. photodetector; Time-resolved saturation dynamics;

Inorganic–organic hybrid metal complexes: 24-membered hexaazamacrocyclic dinuclear nickel complexes hybridized with CdBr4 2− by Deyuan Kong; Xiang Ouyang; Joseph Reibenspies; Abraham Clearfield; Arthur E. Martell (873-878).
An unexpected dinuclear nickel complex was obtained with [CdBr4]2− as a counter ion. In the homodinuclear nickel complex, two different coordination environment entities were observed. One of these was a five-coordinated dinuclear species [Ni(1B)2C26H40N6O2], the other was a six-coordinated dinuclear species [Ni(1A)2C26H40N6O2(H2O)2]. In [Ni(1A)2C26H40N6O2(H2O)2], nickel ion was coordinated to three nitrogen atoms, one phenolic oxygen from macrocyclic ligand, and with one exogenous water molecule to complete an octahedron. In [Ni(1B)2C26H40N6O2], each nickel ion was five-coordinated without solvent interaction. [CdBr4]2− anions were located in the lattice and served as hybrid bridge to connect two different molecules and form two layer arrays along c axis. The whole molecule is described as an ion pair with two-dimensional hydrogen bonding network. The average bond lengths of Ni–N and Ni–O(phenolic oxygen) are 2.083, 2.028 Å.The 24-membered macrocyclic mononuclear cadmium complex reacts with Ni(ClO4)2 in solution and unexpected dinuclear nickel complex was obtained with [CdBr4]2− as counter ions. In the homodinuclear nickel complex, two different coordination environmental entities were observed. One of these is a five-coordinated dinuclear species, the other is a six-coordinated dinuclear species [Ni(1A)2C26H40N6O2(H2O)2]. In [Ni(1A)2C26H40N6O2(H2O)2], nickel ion is coordinated to three nitrogen atoms, one phenolic oxygen from the macrocyclic ligand, and with one exogenous water molecule to complete an octahedron. In [Ni(1B)2C26H40N6O2], each nickel ion is five-coordinated without solvent interaction. [CdBr4]2− anions are located in the lattice and serve as hybrid bridges to connect two different molecules and form two layer arrays along the c axis. The whole molecule is described as an ion pair with a two-dimensional hydrogen bonding network. The average bond lengths of Ni–N and Ni–O(phenolic oxygen) are 2.083, 2.028 Å.
Keywords: Macrocyclic; Dinuclear nickel complex; Inorganic; Hybrid; Crystal structure;

η1-Papical and η1-Pbasal coordination of the P4X3 (X=S, Se) molecules toward 16-e metal fragments by Massimo Di Vaira; Isaac de los Rios; Fabrizio Mani; Maurizio Peruzzini; Piero Stoppioni (879-880).
The bonding modes of the intact P4X3 (X=S, Se) cage molecules toward 16-e ruthenium(II) and rhodium(I) metal fragments have been investigated. Depending on the conditions, coordination through the apical atom of the cage, through a basal P, or both modes contemporarily present have been detected.

New tri- and tetranuclear transition metal spin clusters incorporating a versatile polydentate Schiff base ligand by Colette Boskovic; Eduard Rusanov; Helen Stoeckli-Evans; Hans U. Güdel (881-886).
A trinuclear Fe(III) complex [Fe3(OAc)3L3] (1), a tetranuclear Mn(III) complex [Mn4Cl4L4] (2) and a tetranuclear Ni(II) complex [Ni4(MeOH)4L4] (3) have been synthesized from the reaction of simple metal salts with ligands derived from salicylidene-2-ethanolamine (H2L). Structural characterization of the three complexes reveals distinctly different topologies, despite the similar coordination modes of the ligand L2−. Preliminary magnetochemical studies have been performed and reveal spin ground states of S=1/2,8 and 4 for complexes 1, 2 and 3, respectively.
Keywords: Transition metal spin clusters; Schiff base ligands; Trinuclear complexes; Tetranuclear complexes; Crystal structures;

Mesogenic Pd(II) complexes based on 3-substituted pyrazol ligands by M.C. Torralba; M. Cano; J.A. Campo; J.V. Heras; E. Pinilla; M.R. Torres (887-890).
A new family of linear Pd(II) complexes based on pyrazoles containing long-chain substituents at the third position has been prepared and their mesomorphic properties studied. The crystalline structure of one of these compounds is described as a representative example of a very elongated and straight molecule.
Keywords: Long-chain 3-substituted pyrazoles; Mesomorphism; Palladium–pyrazole complexes;

Electrochemical parametrization of a series of penta- and tetradentate EDTA complexes of ruthenium by Reginaldo C Rocha; Francisca N Rein; Henrique E Toma (891-896).
This paper reports on the electrochemical parametrization of a series of mono- and disubstituted ruthenium–EDTA complexes (EDTA = ethylenediamine-N,N,N ,N -tetraacetate ligand) on the basis of Lever’s parameters (E L). The electrochemical parameters for 45 ligands with unknown E L have been compiled.
Keywords: Ruthenium; Ethylenediaminetetraacetate; Redox potentials; Lever parameters; Electrochemical correlations;

The allyl rhenium complex Re(CO)43-C3H5) (1) reacts with the amino alcohols 2-amino ethanol, 1-amino-propane-2-ol, 2-amino phenol and 2-amino benzyl alcohol (2ad) to give the dimeric μ2-O-bridged tricyclic aminoalkoxy complexes of rhenium of the type [(CO)3Re(μ2-ONH2)]2 (3ad). The acidic NH2 ligand undergoes a condensation reaction with acetone at r.t. forming the corresponding ketimine complexes [(CO)3Re(μ2-ON=CMe2)]2 (4ad). The compounds have been characterized by spectroscopic (IR, NMR, MS), analytical (C, H, N) and X-ray diffraction analyses (4ad).
Keywords: Rhenium complexes; Ketimine complexes; Tricyclic complexes; Condensation reaction; β-Amino alcohol; X-ray;

Kinetics and mechanism of oxidation of hypophosphorous acid by peroxomonosulphate in acid aqueous medium by S. Dubey; Shalini Hemkar; C.L. Khandelwal; P.D. Sharma (903-908).
The reaction is second order – first order with respect to each reactant. Rate is independent of ionic strength, hydrogen ion concentration benzene and t-butyl alcohol, respectively. The possibility of any involvement of OH and SO 4 free radicals has been eliminated. Activation parameters such as energy and entropy of activation have been calculated to be (75±5)  kJ mol −1 and (−45±2)  J K −1   mol −1 , respectively. A probable reaction mechanism has been suggested.
Keywords: Kinetics; Oxidation; Hypophosphorous acid; Peroxomonosulphate;

Nanosecond multiphoton ionisation of jet-cooled ferrocene by Sergey Yu Ketkov; Heinrich L Selzle; Edward W Schlag; Georgy A Domrachev (909-912).
The (Cp)2 Fe +  (Cp=η 5 -C 5 H 5) cations have been obtained in surprisingly high yield by resonance two-colour multiphoton excitation of ferrocene in a jet-cooled molecular beam with tunable nanosecond lasers. The intermediate electronic levels lie in the region of the lowest Rydberg p absorption band. The ion excitation spectrum reveals resolved vibronic structure of the 3d z 2→R4p x,y transition. The distance between the vibronic components (320 cm−1) corresponds to the metal–ligand stretching frequency in the Rydberg state.
Keywords: Ferrocene; Multiphoton ionisation; Rydberg states; Laser spectroscopy;