Inorganic Chemistry Communications (v.8, #8)

Contents List (iii-ix).

A three-dimensional iron phosphite, NH 4 · [ Fe 2 II Fe III ( HPO 3 ) 4 ] , has been synthesized under mild hydrothermal conditions and characterized by single crystal X-ray diffraction. The compound forms three-dimensional framework with six-membered channels along the c-axis. Magnetic measurement indicates the anti-ferromagnetic interactions in the title compound.A three-dimensional iron phosphite, NH 4 · [ Fe 2 II Fe III ( HPO 3 ) 4 ] , has been synthesized under mild hydrothermal conditions and characterized by single crystal X-ray diffraction. The compound crystallizes in the monoclinic space group P21/c, with unit cell parameters, a  = 12.4397(3) Å, b  = 10.1642(3) Å, c  = 9.3201(3) Å, and Z  = 4. The compound forms three-dimensional framework with six-membered channels along the c-axis. The Fe center in the framework adopts slightly distorted octahedral coordination geometry and is bridged by the pseudo-pyramidal phosphites. Magnetic measurement indicates the anti-ferromagnetic interactions in the title compound.
Keywords: Hydrothermal synthesis; Iron phosphite; 3D framework; Anti-ferromagnetic;

Unexpected CuIIZnII amine–imine complex obtained by template reaction under “direct synthesis” conditions by Denys V. Shevchenko; Svitlana R. Petrusenko; Vladimir N. Kokozay; Ingrid Svoboda; Jozef Kožı́šek (665-668).
Copper powder reacts with zinc oxide, ammonium chloride, ethylenediamine and methylethylketone in methanol solution to afford an unexpected bimetallic complex with tetradentate ligand containing –CH2–CH(CH3)–C(CH3)= bridge linking the amine residues.Copper powder reacts with zinc oxide, ammonium chloride, ethylenediamine and methyl ethyl ketone in methanol solution to afford a bimetallic complex with the open chain diaminodiaza ligand – 4,5-dimethyl-1,9-diamino-3,7-di-aza-nona-3-ene (L1) containing the –CH2–CH(CH3)–C(CH3)= bridge linking the amine residues. The origin of the bridge was shown to be a result of template condensation of methyl ethyl ketone and formaldehyde arisen in the process of oxidation of methanol over copper powder acting in the reaction as both a source of metal and a catalyst. The crystal structure of Cu(L1)ZnCl4 was determined by X-ray diffraction and represents the first example of L1 to be crystallographically characterized.
Keywords: Direct synthesis; Template synthesis; Cu/Zn complex; Amine–imine ligand;

Two unprecedented 3-D lanthanide coordination polymers with intertwined double and triple helical structures and 1-D tubular channels have been synthesized based on lanthanide metals and IDC building blocks.Two new three-dimensional lanthanide coordination complexes, [Ln2(IDC)2(H2O)3] · 1.5H2O (Ln = Sm (1), Eu (2), IDC = 4,5-imidazoledicarboxylate), have been prepared by hydrothermal reaction of Ln2O3, H3IDC at 140 °C and characterized by single-crystal X-ray diffraction analysis. To our knowledge, they represent the first examples of having intertwined lanthanide double and triple helical motifs and nanosized tubular channels. In addition, compound 2 exhibit red photoluminescence at room temperature.
Keywords: Helix; Hydrothermal reaction; Lanthanide; Luminescence;

A planar silver complex of 2,2′:6′,2″:6″,2‴-quaterpyridine by Daniela Belli Dell’Amico; Fausto Calderazzo; Matteo Curiardi; Luca Labella; Fabio Marchetti (673-675).
[Ag(qtpy)][ClO4], recrystallized from DMF solutions by slow condensation of acetone vapors has been structurally characterized. In each silver-containing cation, the four nitrogen atoms of the ligand are substantially coplanar, embedding the silver atom. Cations are packed in stacks with distances between the planes of adjacent complexes being alternatively 3.39 and 3.38 Å.The silver(I) complex of 2,2′:6′,2″:6″,2‴-quaterpyridine (qtpy) of formula [Ag(qtpy)][ClO4] was obtained in DMF either by reacting AgClO4 with qtpy or from a ligand redistribution between [Zn(qtpy)2][ClO4]2 and AgBF4. In the solid state the product contains mononuclear substantially planar silver-containing cations, the distances between adjacent planes being alternatively 3.39 and 3.38 Å. Pairs of cations are packed in zig-zag chains, with Ag⋯Ag distances of 3.34 Å being alternated to longer ones (4.70 Å).
Keywords: Polypyridine; Silver complexes; Crystal structure;

Synthesis and characterization of a novel Gd(III)–Cu(II) dinuclear adduct by Greg Brewer; Cynthia Brewer; W. Robert Scheidt; Maoyu Shang (676-679).
The reaction of Cu(2,2-oxomac) with Gd(hfa)3 yields a Gd(III)–Cu(II) dinuclear complex with an oxamide bridge between copper (II) and gadolinium (III). The gadolinium atom adopts a tricapped trigonal prismatic geometry.Two novel Gd(III)–Cu(II) dinuclear complexes have been prepared by the acid–base reaction between Gd(hfa)3 and Cu(2,2-oxomac) (1, Cu(2,2-oxomac)Gd(hfa)3) and between Gd(hfa)3 and Cu(3,2-oxomac) (2, Cu(3,2-oxomac)Gd(hfa)3). These complexes have been characterized by elemental analysis and infrared spectroscopy. The structure of 1 has been determined by X-ray diffraction. The copper atom is square pyramidal, bound to the four planar nitrogen atoms of the macrocycle and weakly bound to the oxygen atom of a dimethylformamide (dmf) molecule. The gadolinium atom is at the center of a tricapped trigonal prism. The nine-coordinate gadolinium atom is bound to six oxygen atoms of three hfa ligands, the two oxamide oxygen atoms of the copper macrocycle, and one oxygen atom of a second coordinated dmf molecule. Unsymmetric binding of the copper macrocycle to gadolinium leads to a distortion in the bridging atoms not observed in reactions of the copper macrocycles with transition metal hfa’s.
Keywords: Tricapped trigonal prismatic; Gadolinium; Dinuclear;

A new polymeric copper(II) complex containing pyrazine-2-carboxyamide (pzca): Synthesis and crystal structure of {[Cu(pzca)(CH3CN)3](ClO4)2  · H2O} n by Stefania Tanase; Patricia Marqués Gallego; Elisabeth Bouwman; René de Gelder; Jan Reedijk (680-683).
The synthesis and the crystal structure of the new coordination polymer, {[Cu(pzca)(CH3CN)3](ClO4)2  · H2O} n is reported. The compound presents a two-dimensional extended structure as a result of the hydrogen bonding interactions involving the amino functional group of the pzca molecule, the water molecule and the perchlorate anions.The copper(II) polymeric complex {[Cu(pzca)(CH3CN)3](ClO4)2  · H2O} n (1) (pzca stands for 2-pyrazine carboxamide) has been synthesized and characterized by X-ray crystal structure determination. The copper(II) ion has an elongated octahedrally geometry due to the coordination of three donor atoms from two different pzca ligands and one acetonitrile molecule in the equatorial plane and two acetonitrile molecules in axial positions. The pzca ligand acts as a tridentate with a pyrazine bridge between two Cu(II) ions leading to a Cu⋯Cu separation of 6.7852 Å. Adjacent chains are linked through hydrogen-bonding interactions to generate a two-dimensional layer structure.
Keywords: Copper; Pyrazine amide; Hydrogen bonds;

[Ru(2,2′-bipy)3]2[Bi4I16]: A bimetallic inorganic–organic complex consisting of a d-metal coordination cation and a polynuclear iodobismuthate anion by Andrea M. Goforth; James R. Gardinier; Mark D. Smith; LeRoy Peterson; Hans-Conrad zur Loye (684-688).
The bimetallic inorganic–organic complex salt [Ru(bipy)3]2[Bi4I16] was synthesized solvothermally from BiI3 using [Ru(bipy)3]I2  · 4H2O as both a cation source and a halide ion donor. The title compound represents a rare mixed-metal halobismuthate material and offers the unique combination of a photochemically active cation in conjunction with an anionic component derived from the neutral semiconductor BiI3.The crystal structure of [Ru(2,2′-bipy)3]2[Bi4I16] (2,2′-bipy = 2,2′-bipyridine) contains the photochemically active coordination cation [Ru(2,2′-bipy)3]2+ and the large, polynuclear [Bi4I16]4− anion. [Bi4I16]4− consists of four edge-sharing BiI6 octahedra and is derived from the neutral, semiconductor BiI3 by uptake of I. The title compound is a rare example of a mixed-metal halobismuthate material [crystal data C60H48Bi4I16N12Ru2: triclinic, P 1 ¯ , a  = 12.2963(7) Å, b  = 14.0147(8) Å, c  = 14.7234(8) Å, α  = 70.1900(1)°, β  = 69.2010(1)°, γ  = 72.6570(1)°].
Keywords: Bismuth halide; Iodobismuthate; Semiconductor; Mixed-metal system; Supramolecular assembly; Diffuse reflectance UV–Vis;

Structural and spectroscopic properties of bis-3-picolinium 1,8-naphthalimide tetrachlorocuprate by Chandan Tamuly; Nilotpal Barooah; Andrei S. Batsanov; R. Kataky; Jubaraj B. Baruah (689-691).
Significant reduction of fluorescence intensity in bis-3-picolinium 1,8-naphthalimide tetrachlorocuprate with respect to the of 3-picolyl 1,8-naphthalimide is observed whereas in tris-(3-picolyl 1,8-naphthalimide)copper (II)chloride it is enhanced.In bis-3-picolinium 1,8-naphthalimide tetrachlorocuprate reduction of fluorescence intensity with respect to the of 3-picolyl 1,8-naphthalimide is observed but in tris-(3-picolyl 1,8-naphthalimide)copper (II)chloride fluorescence intensity is enhanced.
Keywords: 1,8-Naphthalimide; Tetrachlorocuprate; Fluorescence; Electrochemistry;

Novel infinite hexanuclear zinc coordination polymer with a flexible bipyridyl ligand and its catalytic activity by Jun Yong Lee; Sung Jin Hong; Cheal Kim; Sung-Jin Kim; Youngmee Kim (692-696).
The reaction of Zn(OTf)2 with 1,3-bis(4-pyridyl)propane results in a novel infinite hexanuclear coordination polymer, [Zn6(OH)8{(NC5H4)2C3H6}4](OTf)4  · 3H2O, which was found to carry out the catalytic transesterification of esters with methanol at room temperature under the mild homogeneous conditions.The reaction of Zn(OTf)2 with 1,3-bis(4-pyridyl)propane results in a novel infinite hexanuclear coordination polymer, [Zn6(OH)8{(NC5H4)2C3H6}4](OTf)4  · 3H2O, which was found to carry out the catalytic transesterification of esters with methanol at room temperature under the mild homogeneous conditions.
Keywords: Zn(II) coordination polymer; Bipyridyl ligand; Transesterification; Crystal structure;

Screening of ATP hydrolysis by Zr(IV) and Eu(III) complexes by Malgorzata Jagoda; Roland Krämer (697-699).
Complexes of Zr4+ ions with chelating aminoalcohol and aminocarboxylate ligands efficiently catalyze the hydrolysis of ATP. An automated, colorimetric assay which is compatible with the presence of this high-valent metal ion was used to screen catalytic activities.The dephosphorylation of adenosine triphosphate (ATP) by various zirconium (IV) and europium (III) complexes is described. Release of phosphate was followed by an automated, robotics-based colorimetric assay which is compatible with the presence of these high-valent metal ions.
Keywords: ATP; Zirconium; Europium; Screening; Phosphate;

Unusual perchlorate binding in heptacoordinated cadmium(II)thiocyanate containing a pentadentate Schiff base by Sk Hafijur Rahaman; Rajarshi Ghosh; Golam Mostafa; Barindra Kumar Ghosh (700-703).
A novel heptacoordinated cadmium(II)thiocyanate complex [Cd(bpbd)(NCS)(ClO4)] (1) has been synthesized and X-ray crystallographically characterized, which shows unusual perchlorate binding along with C–H⋯O hydrogen bonding and C–H⋯π interaction leading to a 2D sheet.A new Schiff base, N,N′-(bis(pyridin-2-yl)benzylidene)diethylenetriamine (bpbd), has been used to synthesise a novel heptacoordinated cadmium(II)thiocyanate complex [Cd(bpbd)(NCS)(ClO4)] (1). Crystal structure analysis of 1 reveals cadmium(II) centre in a distorted pentagonal bipyramid environment with perchlorate binding, C–H⋯O hydrogen bonding and C–H⋯π interaction leading to a 2D sheet. 1 displays intraligand 1(π–π*) fluorescence and intraligand 3(π–π*) phosphorescence in glassy solutions (MeOH at 77 K).
Keywords: Cadmium(II)thiocyanate; Schiff base; X-ray structure; Supramer; Luminescence;

Synthesis and structure of a novel heterotrimetallic helical chain polymer {O2MoS2(CuCN)Ni(1,10-phen)2} n by Chuan-Peng Cui; Sheng-Min Hu; Jian-Jun Zhang; Wen-Xin Du; Xin-Tao Wu (704-707).
The title heterotrimetallic compound has a structural motif of “8”-like helical chain. It uses CN group to bridge Ni and Cu atoms, while μ2-S and μ2-O atoms to bridge Mo and Cu, Mo and Ni atoms respectively.A novel 1-D heterotrimetallic polymer {O2MoS2(CuCN)Ni(1,10-phen)2} n containing cyanide ligands was synthesized and characterized by single-crystal X-ray diffraction studies. This compound can be described as an “8”-like helical chain that the CN ligands are bridged between Ni and Cu atoms while the μ2-S and μ2-O atoms are bridged between Mo and Cu and Mo and Ni atoms, respectively.
Keywords: Cyanide; Nickel; Copper; Molybdenum; Heterometalate;

Syntheses, crystal structures and magnetic properties of two new 3-cyanobenzate coordination complexes by Yan Li; A-Qing Wu; Fa-Kun Zheng; Ming-Lai Fu; Guo-Cong Guo; Jin-Shun Huang (708-712).
The Cu(II) and Cd(II) 3-cyanobenzate complexes have been synthesized and structurally characterized. Variable-temperature magnetic susceptibility data indicate that the Cu(II) polymeric complex exhibits antiferromagnetic interactions.Two new 3-cyanobenzate complexes, [Cu(3-cba)2(Py)(H2O)] n 1 and [Cd(3-cba)2(Py)2(H2O)] 2 (3-cba = 3-cyanobenzate, Py = pyridine), were synthesized and structurally characterized by single-crystal X-ray diffraction. Three different coordination modes of 3-cba group exist in the two obtained complexes, which results in different molecular architectures: 1 with a 1-D chained structure and 2 with an isolated configuration. Variable-temperature magnetic susceptibility data show the presence of antiferromagnetic interactions in 1.
Keywords: 3-Cyanobenzate complex; Crystal structure; Magnetic properties; Hydrogen bonds; π–π Stacking;

Fast interconversion between the trigonal boronic acid and the tetrahedral boronate ion: k 1  = 7.9 × 104 M−1  s−1 at 25 °C in acetonitrileThe rate constant, k 1, for the following addition reaction between 4-isopropyltropolonate (ipt) and meta-nitrophenylboronic acid (m-NO2PhB(OH)2) in acetonitrile was measured at various temperatures by using a low-temperature stopped-flow spectrophotometer: m - NO 2 PhB ( OH ) 2 + ipt - ⇌ k - 1 k 1 m - NO 2 PhB ( OH ) 2 ( ipt ) - ; k 1  = 7.9 × 104M−1  s−1 at 25 °C, Δ H 1 ∗ = 34 . 7 ± 1 . 0 kJ mol - 1 , Δ S 1 ∗ = - 34 . 8 ± 3 . 8 J mol - 1 K - 1 , which indicates that the interconversion between the trigonal boronic acid and the tetrahedral boronate ion is much faster than the chelate formations for the complexation of boronic acid with bidentate ligands, but much slower than the diffusion-controlled reactions.
Keywords: m-Nitrophenylboronic acid; 4-Isopropyltropolonate; Interconversion; Kinetics;

A supported Mn(III) catalyst based on d-glucose in the asymmetric epoxidation of styrenes by Carmela Borriello; Raffaella Del Litto; Achille Panunzi; Francesco Ruffo (717-721).
The preparation of the supported Mn(III)-complex 3 derived from d-glucose is described. The activity of the anchored catalyst in the asymmetric epoxidation of styrenes has been investigated and compared to that of corresponding homogeneous compounds.A strategy for the preparation of a supported ‘salen-type’ Mn(III) catalyst derived from d-glucose is described. The compound has been prepared by introducing the ligand functions at positions 2 and 3 of the sugar, which has been subsequently anchored to a CHO-modified Wang resin through formation of a 4,6-O-benzylidene ring. The activity of the catalyst in the asymmetric epoxidation of styrenes has been investigated by using four different oxidants.
Keywords: Sugars; Manganese; Styrene; Oxidation; Enantioselectivity; Supported catalysis;

Rare 4.82 net in a fluorescent Cd-organic framework by Yao Kang; Jian Zhang; Zhao-Ji Li; Ye-Yan Qin; Yuan-Gen Yao (722-724).
A novel Cd(II) polymer with rare two-dimensional 4.82 net was successfully synthesized and structurally characterized.The reaction of CdCl2 with picolinic acid in the presence of isonicotinic acid in DMF yielded a Cd(II) complex, [Cd(pyc)(μ-Cl)] n (1; pyc = 2-pyridinecarboxylate), containing a rare two-dimensional 4.82 net constructed by Cd ions, μ-O and μ-Cl bridges. It exhibits photoluminescence at 440 nm (λ ex  = 322 nm).
Keywords: Cd complex; Topology; Photoluminescence;

An unexpected Sn–Ph cleavage by mercaptoacetic acid by Xueqing Song; Guiyun Zhong; Qinglan Xie; George Eng (725-728).
The reaction of triphenyltin chloride and mercaptoacetic acid under mild reaction conditions in the presence of an amine resulted in the cleavage of a Sn–Ph bond. This cleavage reaction was not observed when triphenyltin hydroxide or other triorganotin chlorides were employed. A possible pathway was proposed for the Sn–Ph cleavage.The reaction of triphenyltin chloride and mercaptoacetic acid under mild reaction conditions in the presence of an amine resulted in the cleavage of a Sn–Ph bond. This cleavage reaction was not observed when triphenyltin hydroxide or other triorganotin chlorides were employed. A possible pathway was proposed for the Sn–Ph cleavage. This is a first report of a mercaptoacetate ligand cleavaging Sn–Ph bonds under mild reaction conditions. It is also the first report of using 3 J(119Sn–1H) (–Sn–S–CH2) coupling constants to differentiate sulfur containing organotin compounds.
Keywords: Sn–C cleavage; Mercaptoacetic acid; Crystal structure; Coupling constants;

A new molecular oxide with a Pt2Mo2O8 core and its two conformers by Keiki Noro; Yoshiki Ozawa; Atsushi Yagasaki (729-731).
The first Pt molecular oxide that incorporates a hetero element has been synthesized by reacting [(Me3P)2Pt](NO3)2 with Na2MoO4 and its two different conformers have been structurally characterized.The first Pt molecular oxide that incorporates a hetero element has been synthesized by reacting [(Me3P)2Pt](NO3)2 with Na2MoO4 and its two different conformers have been structurally characterized.
Keywords: Molecular oxide; Polymolybdate; Polynuclear platinum complex;

The structure of {[Mn(μ-ox)(H2O)2] · H2O} n could be described as one-dimensional chain structure in which Mn atoms are bis-bidentately bridged by oxalates in cis-configuration. Magnetic interactions mediated by bridging oxalates and interchain hydrogen bonds result in the long-range antiferromagnetic ordering below T N  = 2.82(5) K, which is determined by the specific heat measurement.The previously known manganese (II) oxalate trihydrate, MnC2O4  · 3H2O or {[Mn(μ-ox)(H2O)2] · H2O} n (1) (ox = oxalate), has been synthesized by a novel method with the formation of single crystals, which are suitable for X-ray determination. The result shows that Mn atoms are bis-bidentately bridged by oxalates in cis-configuration to form a one-dimensional chain structure. Magnetic measurement reveals intra-chain antiferromagnetic coupling between MnII ions in 1 with J  = −1.07 cm−1. Specific heat measurement exhibits a sharp peak at T N  = 2.82(5) K for 1 due to long-range antiferromagnetic ordering, for which the interchain hydrogen bonds should be responsible.
Keywords: Manganese (II) complex; Oxalate ligand; One-dimensional chain; Crystal structure; Antiferromagnetic properties.;

Complexation of copper (II) perchlorate with cis,cis-1,3,5-cyclohexanetricarboxylic acid (CTA) and cis,trans-1,3,5-triaminocyclohexane (trans-tach) in the presence of triethylamine leads to the formation of a dinuclear metallacycle; [Cu2(trans-tach)2(CTA)2] · 7H2O, (1). The crystal structure of 1 shows an extended hydrogen bonded network comprising linear chains of metallacycles (blue arrows) running perpendicular to solvent occupied channels (green arrows).Complexation of copper (II) perchlorate with cis,cis-1,3,5-cyclohexanetricarboxylic acid (CTA) and cis,trans-1,3,5-triaminocyclohexane (trans-tach) in the presence of triethylamine leads to the formation of a dinuclear metallacycle; [Cu2(trans-tach)2 (CTA)2] · 14H2O (1). The crystal structure of 1 shows an extended hydrogen bonded network comprising linear chains of metallacycles running perpendicular to solvent occupied channels.
Keywords: Supramolecular; Coordination chemistry; Metallacycles; Hydrogen bonding; Rigid aliphatic ligands; Metal organic frameworks; Self assembly;

Oligomerization of Yb(III)-substituted Dawson polyoxotungstates by oxalato ligands by Pierre Mialane; Anne Dolbecq; Jérôme Marrot; Francis Sécheresse (740-742).
The connection of Wells–Dawson [Yb(H2O)4(P2W17O61)]7− polyoxometalate units by oxalato ligands has afforded the tetrameric (NH4)29K5[{Yb(P2W17O61)}4(C2O4)3(H2O)4] · 95H2O complex (1). Complex 1 has been characterized in the solid state by single crystal X-ray diffraction. 31P NMR studies have shown the dissociation of 1 in solution.The connection of Wells–Dawson [Yb(H2O)4(P2W17O61)]7− polyoxometalate units by oxalato ligands has afforded the tetrameric (NH4)29K5[{Yb(P2W17O61)}4(C2O4 )3(H2O)4] · 95H2O complex (1). Complex 1 has been characterized in the solid state by single crystal X-ray diffraction. 31P NMR studies have shown the dissociation of 1 in solution.
Keywords: Oxalate; Polyoxometalate; Tetramer;

Preparation and structural characterization of a dicopper prehelicate by Edwin C. Constable; Catherine E. Housecroft; Markus Neuburger; Silvia Schaffner; Ellen J. Shardlow (743-745).
[Cu2(PPh3)2(μ-I)(μ-L)]I (L = 4′-(4-ethynylphenyl)-2,2′:6′,2″-terpyridine) has been isolated from the reaction of L with trans-[PtI2(PEt3)2] and CuI. L adopts a helical twist that parallels that found in related double helicates.In the reaction of 4′-(4-ethynylphenyl)-2,2′:6′,2″-terpyridine (3) with trans-[PtI2(PEt3)2] and CuI, ligand 3 scavenges Cu(I) and forms [Cu2(PPh3)2(μ-I)(μ-3)]I, structural characterization of which shows that ligand 3 adopts a helical twist that parallels that found in related double helicates.
Keywords: Copper(I); Helicate; Oligopyridine ligand; Alkyne; Dinuclear;

Coordination of Cu2+ and N-(2-hydroxylbenzyl)amino acids (H2sgly and H2sala) together with 2,2′-bipyridine as co-ligand led to two new helical coordination polymers. Their crystal structures are similar. But their magnetic behaviors are different; the complex from H2sgly shows ferromagnetic property while that from H2sala displays paramagnetic behavior.Two new helical Cu(II) coordination polymers, [Cu(2,2′-bpy)(Hsgly)]Cl · 2H2O(H2sgly =  N-(2-hydroxylbenzyl)glycine) (1) and [Cu(2,2′-bpy)(Hsala)](NO3) · 2H2O(H2sala =  N-(2-hydroxylbenzyl)-l-alanine) (2) were synthesized. Single crystal X-ray diffraction analysis indicated that both complexes showed helical chains arrangement of Cu(II) centers bridged by carboxyl groups. The magnetic measurements showed complex 1 exhibited ferromagnetic interaction while there was no interaction between the Cu(II) centers in complex 2.
Keywords: Helical chain; Copper(II) complexes; Crystal structure; Amino acid; Magnetic property;

A linear bifunctionalized organoimido derivative of hexamolybdate has been synthesized by a convenient synthetic route, in which two imido groups are bounded to two terminal positions of a hexa-molybdate anion in an unusual trans fashion, thus paving the way for the synthesis of main-chain-POM-containing linear hybrid polymers.A new disubstituted imido derivative [Bu4N]2[Mo6O17(NAr)2] (1) (Ar = 2,4-(CH3)2C6H3), has been synthesized under a mild and convenient reflux reaction of [Bu4N]2[Mo6O19], 2,4-dimethylaniline, and DCC, and characterized by IR spectroscopy, elemental analysis, UV–vis absorption spectroscopy, and single-crystal X-ray diffraction. The most interesting characteristic of 1 is that its anion segment is linear and centrosymmetric with two imido groups occupying two terminal positions of hexamolybdate in an unusual trans fashion. This is the first trans-bis(imido)hexamolybdate prepared via a convenient synthetic route.
Keywords: Polyoxometalates; Hexamolybdate; Organoimido derivatives; Functionality;

A double-bridged cofacial dinuclear complex of palladium(II), bis (μ-acetamido-O,N){bis[(1,10-phenanthroline)palladium(II)]}bis-tetrafluoroborate was obtained by hydrolysis of the coordinated acetonitrile in the complex [Pd(phen)(MeCN)2](BF4)2. Spectroscopic and structural characterizations are reported.Palladium mediated hydrolysis of coordinated acetonitrile in the complex [Pd(phen)(MeCN)2](BF4)2, under basic conditions, affords the dinuclear palladium(II) species bis(μ-acetamido-O,N) {bis[(1,10-phenanthroline)palladium(II)]}bis-tetrafluoroborate.X-ray crystallographic analysis of this species (structure a) and of its acetonitrile solvate (structure b) shows that the syn isomer of the complex is formed and that dimers aggregate to form discrete tetrameric units (Pd–Pd intradimer distances 2.875(3) Å (a), 2.852(1) Å (b) and Pd–Pd* interdimer distances 3.213(3) Å (a), 3.079(1) Å (b)). The correlation between syn-coordination mode and aggregation of dimers is discussed.
Keywords: Palladium; Dinuclear complexes; Hydrolysis; Nitriles;