Inorganic Chemistry Communications (v.10, #1)

Contents List (iii-x).

The reaction of [Pd{PhP(C6H4-2-S)2}(PPh3)] (1) with Ph2CH2CH2Ph2 in dichloromethane affords complex [Pd{PhP(C6H4-2-SCH2Cl) (C6H4-2-S)} (Ph2PCH2CH2PPh2)]Cl (2) as product of the phosphine substitution, the hemilabile properties of the ligand [PhP(C6H4-2-S)2]2− and the CH2Cl2 activation by the de-ligated thiolate moiety.The stoichiometric reaction of [Pd{PhP(C6H4-2-S)2}(PPh3)] (1) with Ph2CH2CH2Ph2 in dichloromethane (CH2Cl2) as solvent, affords complex [Pd{PhP(C6H4-2-SCH2Cl)(C6H4-2- S)}(Ph2PCH2CH2PPh2)]Cl (2). This specie, being the result of the nucleophilic reaction of a de-ligated thiolate moiety from the fragment [Pd{PhP(C6H4-2-S)2}] with dichloromethane (chloromethylation).
Keywords: Chloromethylation; Dichloromethane activation; Pincer complexes; Palladium complexes; Crystal structures; Hemilability;

A novel one-dimensional (1D) coordination polymer {[Cu2(amtrz)4(1,1-μ-NCS)2](ClO4)2  · H2O} n (1) (amtrz = 4-amino-1,2,4-triazole) was synthesized and structurally characterized. The 1D chains of 1 are linked via short intermolecular S⋯S interactions to form a 3D supramolecular architecture with 1D channels along c direction, while water molecules and perchlorate anions were encapsulated in the channels. Variable-temperature magnetic susceptibilities (2–300 K) shows antiferromagnetic interactions with J  = −51.3 cm−1.A novel one-dimensional (1D) coordination polymer {[Cu2(amtrz)4(1,1-μ-NCS)2](ClO4)2  · H2O} n (1) (amtrz = 4-amino-1,2,4-triazole) was synthesized and structurally characterized. The 1D chains of 1 are linked via short intermolecular S⋯S interactions to form a 3D supramolecular architecture with 1D channels along c direction, while water molecules and ClO 4 - anions were encapsulated in the channels. Variable-temperature magnetic susceptibilities (2–300 K) shows antiferromagnetic interactions with J  = −51 cm−1.

Two asymmetric dithioether ligands with cyclohexyl (L 1) and phenyl (L 2) end-groups were synthesized. Reaction of L 1 with copper(I) iodide afforded a 1D channel-type coordination polymer {[Cu4I4(L 1)2](CH3CN)0.5} n (1) interconnected by cubane-type tetranuclear Cu4I4 cluster units. Whereas, 2D brick-wall-type coordination polymer [CuI(L 2)] n (2) with rhomboid dinuclear Cu–I2–Cu nodes was isolated from the reaction of L 2 with copper(I) iodide.Two asymmetric dithioether ligands with cyclohexyl (L 1) and phenyl (L 2) end-groups were synthesized. Reaction of L 1 with copper(I) iodide afforded a 1D channel-type coordination polymer {[Cu4I4(L 1)2](CH3CN)0.5} n (1) interconnected by cubane-type tetranuclear Cu4I4 cluster units. Whereas, a 2D brick-wall-type coordination polymer [CuI(L 2)] n (2) with rhomboid dinuclear Cu–I2–Cu nodes was isolated from the reaction of L 2 with copper(I) iodide.
Keywords: Copper(I) iodide; Coordination polymer; Dithioether ligand; Crystal structure; Supramolecular assembly;

YI3(Pr i OH)4 (1), obtained from the reaction between yttrium chips and iodine in isopropanol, reacted with dioxygen to give a dinuclear ionic species [Y2I2201-O2)2(Pr i OH)8][I]2 (2). It is the first structurally characterized yttrium superoxide derivative as well as the first superoxide derived from an iodide. In addition, it displays a rare μ201 bonding mode of O 2 − . DFT calculations indicate that this molecule is stable in its high spin triplet state.YI3(Pr i OH)4 (1), obtained from the reaction between yttrium chips and iodine in isopropanol, reacts with dioxygen to give a superoxide bridged dinuclear ionic species [Y2I2201-O2)2(Pr i OH)8][I]2 (2). The ligand exchange reaction of 1 with N,N-dimethylaminoethanol (dmaeH) afforded YI3(dmaeH)4 (3). Complex 2 is the first structurally characterised yttrium superoxide derivative. In addition, it displays a rare μ201 bonding mode of O 2 − , unknown in transition metal chemistry. 2 is also the first example of a superoxide derived from a metal iodide. The DFT calculations on a model compound, where the Pr i OH molecules of 2 are replaced by water molecules, i.e. for [Y2I2201-O2)2(H2O)8][I]2 (2a), show that this molecule is stable in its high spin triplet state with the SOMO–LUMO gap being 3.7 eV.
Keywords: Superoxide; Yttrium; Structure; Iodide; Dioxygen activation;

Preparation of highly concentrated aqueous solution of sodium borate by Isao Tsuyumoto; Tomokazu Oshio; Kenji Katayama (20-22).
Sodium borate aqueous solution containing 5.24 mol/kg of boron at 20 °C, which is more than twice the most soluble known borate solution (Na2O · B2O3  · 8H2O, 2.49 mol/kg at 20 °C), was prepared by adjusting the Na/B ratio at 0.22 (pH 6.9). Analysis of the solution using the Raman spectroscopy and the ACI/MS suggested the formation of polyborate ions B( n O2n−8(OH)18−n 2−, n  = 8–15).A highly concentrated aqueous solution of sodium borate with 5.24 mol/kg of boron was prepared at 20 °C by adjusting the Na/B ratio at 0.22 (pH 6.9). This is more than twice more concentrated than the most soluble known borate solution (Na2O · B2O3  · 8H2O, 2.49 mol/kg at 20 °C). Analysis using the Raman spectroscopy and the APCI/MS (atmospheric pressure chemical ionization/mass spectrometry) suggested the formation of polyborate ions such as B 9 O 10 ( OH ) 9 2 - , B 10 O 12 ( OH ) 8 2 - , B 11 O 14 ( OH ) 7 2 - , B 12 O 16 ( OH ) 6 2 - .
Keywords: Boron; Borate; Fire retardant; Raman; Sodium; Boric acid; Polyborate;

A novel 1D molybdenum oxide ribbon bridged by pyridine-4-carboxylic ligands: [(C6H4NO2) Mo2O5OH] by Wan-sheng You; Xin Guo; Xiao-li Yu; Cui-ying Huang; Lan-cui Zhang; Zhen-gang Sun (23-26).
The structure of [(C6H4NO2) Mo2O6] consists of MoO6 octahedra and pyridine-4-carboxylic ligands. MoO6 octahedra share their adjacent equatorial edges, forming a new 1D ribbon-like molybdenum oxide framework. Pyridine-4-carboxylic ligands are bridged to the molybdenum sites up and down along the ribbon.A novel 1D organic–inorganic hybrid compound [(C6H4NO2)Mo2O5OH] 1 has been synthesized hydrothermally and characterized by single crystal X-ray diffraction, IR, and thermogravimetric analysis. The structure of [(C6H4NO2)Mo2O5OH] consists of {MoO6}octahedra and pyridine-4-carboxylic ligands. {MoO6} octahedra share their adjacent equatorial edges, forming a new 1D ribbon-like molybdenum oxide framework. Pyridine-4-carboxylic ligands are bridged to the molybdenum sites up and down along the ribbon.
Keywords: Molybdenum oxides; Pyridine-4-carboxylic groups; Hydrothermal synthesis;

Diversity of carboxylate coordination in two novel zinc(II) cinnamate complexes by V. Zeleňák; I. Císařová; P. Llewellyn (27-32).
Two novel mixed-ligand zinc(II) complex compounds [Zn(cinn)2(mpcm)] n (1) and [Zn(p-HO- cinn)2(nia)(H2O)2] · H2O (2) (cinn = cinnamato, mpcm = methyl-3-pyridylcarbamate, nia = nicotinamide) were prepared and characterized. In 1 the cinnamate ligands coordinate as monodentate and bridging (syn–anti), respectively. The syn–anti carboxylate bridges connect the molecules of 1 to infinite polymeric helical chains. The structure of 2 is monomeric. One of the carboxylate oxygens of p-hydroxycinnamate is semi-coordinated (Zn–O = 2.549(2) Å).Two novel mixed-ligand zinc(II) complex compounds [Zn(cinn)2(mpcm)] n (1) and [Zn(p-HO-cinn)2(nia)(H2O)2] · H2O (2) (cinn = cinnamato, mpcm = methyl-3-pyridylcarbamate, nia = nicotinamide) were prepared and characterized by elemental analysis, infrared spectroscopy, single crystal X-ray diffraction and thermal analysis. Diverse modes of carboxylate coordination were found in the complexes. In 1 the cinnamate ligands coordinate as monodentate and bridging (syn–anti), respectively. The syn–anti carboxylate bridges connect the molecules of 1 to infinite polymeric helical chains. The structure of 2 is monomeric. One of the carboxylate oxygens of p-hydroxycinnamate is semi-coordinated (Zn–O = 2.549(2) Å).
Keywords: Zinc; Cinnamate complexes; Nicotinamide complexes; Methyl-3-pyridylcarbamate complexes; 1D coordination chain; Semi-coordination;

Hydrothermal treatment of Co(II) ions, multifunctional phosphonate H3pa (HO2CCH(OH)PO3H2) and organic amine (en) gave [enH2]0.5[Co(pa)(H2O)] · H2O (1), a novel 3D supramolecular network consisting of honeycomb-like layers constructed by CoO6 octahedra and μ3-pa ligand with protonated en and lattice water molecules stabilized between the layers, which exhibits weak ferromagnetism, spin-glass behavior, and metamagnetic behavior at low temperatures.A new cobalt(II) phosphonate, [enH2]0.5[Co(pa)(H2O)] · H2O (1) (H3pa = hydroxy-phosphono-acetic acid, HO2CCH(OH)PO3H2; en = ethylenediamine), has been hydrothermally synthesized and structurally characterized. Compound 1 has a honeycomb-like layer structure which is composed of CoO6 octahedra and μ3-pa ligands with the protonated en and lattice water molecules stabilized between the layers. Magnetic studies indicate that 1 shows weak ferromagnetic behavior, spin-glass behavior, and metamagnetic behavior.
Keywords: Cobalt(II) phosphonate; Hydrothermal synthesis; Magnetic properties;

A novel 4.82 topology of cadmium-sulfate frame work was observed in coordination polymer [CdII(1,4-BIMB) (H2O)2] H2O (1), isolated from solvothermal reaction of BIMB and CdSO4  · 8/3H2O.A complex, [Cd(BIMB)0.5SO4(H2O)2] n  ·  nH2O (1) was synthesized by solvothermal reaction of 1,4-bis(imidazol-1-ylmethy)benzene (BIMB) with CdSO4  · 8/3H2O and was revealed a photoluminescent 3-D metal-organic framework (MOF), assembled from 2-D Cd(II)– SO 4 2 - coordination sheets and trans configured BIMBs.
Keywords: Inorganic network; BIMB; Photoluminescence;

Tris(μ-phenoxo) bridged Cd(II) polymer synthesised from a symmetrical tripodal ligand: A novel observation for heptadentate monocapped trigonal antiprismatic Schiff base complex.A novel one-dimensional cadmium(II) polymer [Cd2(L){HCON(CH3)2}N(CN)2] n (H3L = condensation product of tris(2-aminoethyl)amine and salicylaldehyde) has been achieved from a tripodal Schiff base tris[(2-salicylaldeneimino)ethyl]amine or ‘trensal’. The structure confirmed from single crystal X-ray diffraction analysis reveals that each of the tris(μ-phenoxo) bridged individual Cd(II) dimeric units is interlinked via μ-(1,5) end-to-end (EE) dicyanamide [N(CN)2] ligand framing a wavy chain polymer, which is believed to be the first report of its kind in the literature.
Keywords: Cd(II) polymer; Tris(μ-phenoxo) bridging; μ-(1,5)-Dicyanamide; X-ray crystal structure;

Density functional studies on structure and reactivity of a dinuclear peroxovanadate(V) complex by Diganta Kalita; Ramesh Ch. Deka; Nashreen S. Islam (45-48).
Structure and reactivity of peroxo-bridged divanadate complex [V2O2(O2)3(glycine)2], has been studied by using density functional method.Density functional method is used to investigate the structure and reactivity of peroxo-bridged divanadate complex [V2O2(O2)3(glycine)2]. The results suggest the presence of two types of structurally non-equivalent peroxo groups and formation of hydrogen bonding between the glycine co-ligands in the complex. These observations are in complete agreement with the experimental findings. Density functional reactivity descriptors such as Fukui function and relative electrophilicity identify the bridged peroxo group of the complex as the most reactive one in terms of its susceptibility to attack by a neucleophile. Attempt has been made to correlate the results of the study to the observed reactivity pattern of the complex species in oxidative bromination.
Keywords: Fukui function; Relative electrophilicity; Dinuclear peroxovanadate; Oxidative bromination;

The three dimensional structure of 1 has a novel topological metal-organic framework, which is built up by Zn2+, Cu+ and ligands IN to generate an open-framework with an unusual helical [–Zn(cu)-IN–] n chains along the b axis.The first mixed metal Zn/Cu coordination polymer, [Zn3Cu2(IN)8] (1) (HIN = isonicotinic acid) was synthesized under hydrothermal conditions. The three dimensional structure of 1 has a novel topological metal-organic framework, which is built up by Zn2+, Cu+ and ligands IN to generate an open-framework with an unusual helical [–Zn(Cu)-IN–] n chains along the b axis. The very strong blue fluorescence for 1 can be observed in the solid state.
Keywords: Microporous; Mixed Zn/Cu; Metal-organic open framework; Crystal structure; Blue fluorescence;

A new neutral 2D coordination polymer, {[Ni(pot)2(H2O)2] · 6H2O} n (1) (Hpot = 5-(4-pyridyl)-1,3,4-oxadiazole-2-thione), has been prepared under a mixed solvents medium. Large rectangular channels to trap water molecules were observed in 1, and its gas sorption property has been investigated.A new neutral 2D coordination polymer, {[Ni(pot)2(H2O)2] · 6H2O} n (1) (Hpot = 5-(4-pyridyl)-1,3,4-oxadiazole-2-thione), has been prepared by reacting NiII salt with the Hpot ligand under a mixed solvents medium; 1 possesses large rectangular channels to trap water molecules. It has been characterized by IR and gas sorption property as well as TG analysis.
Keywords: Nickel coordination ploymer; Gas sorption; Channel; 5-(4-Pyridyl)-1,3,4-oxadiazole-2-thione; Unsymmetric ligand; Two-dimensional network;

Reductive nitrosation of methyl amine ligated to a nickel(III) complex by Dror Shamir; Israel Zilbermann; Eric Maimon; Haim Cohen; Dan Meyerstein (57-60).
The reductive nitrosation of amines ligated to high valent transition metal cations, e.g. Ni(III), is a radical process.The reductive nitrosation of amines ligated to high valent transition metal cations, e.g. Ni(III), is a radical process.
Keywords: Reductive nitrosation; NO; Amine ligands; Nickel(III);

Two heptacoordinated dinuclear cadmium(II)pseudohalide complexes of type [Cd(bpbe)(X)2]2  ·  nH2O bpbe =  N,N′-(bis(pyridin-2-yl)benzylidene)ethane-1,2-diamine; X = N 3 - , n  = 2, 1; X = NCS, n  = 0; 2] have been synthesized and characterized by X-ray diffraction measurements. The bridging mode of azide is end-on and thiocyanato bridges are in end-to-end fashion. Ligand bpbe exhibits green fluorescence at room temperature whereas its azido and thiocyanato compounds have a hypsochromic shift in blue wavelength region.Two heptacoordinated dinuclear complexes of the type [Cd(bpbe)(X)2]2  ·  nH2O [bpbe =  N,N′-(bis(pyridin-2-yl)benzylidene)ethane-1,2-diamine; X = N 3 - , n  = 2, 1; X = NCS, n  = 0; 2] are prepared and the structures are solved by X-ray study that reveals interesting variation in bridging motifs of the pseudohalides from bibridged end-on (in 1) to bibridged end-to-end (in 2). The hydrated dinuclear units in 1 pack through O–H…N, C–H…O, and C–H…N hydrogen bonds along with π…π interaction leading to an infinite 1D chain and the dinuclear units in 2 are engaged in π…π interactions resulting a 2D sheet structure. They display intraligand 1(π–π) fluorescence and 3(π–π) phosphorescence in glassy solutions.
Keywords: Cadmium(II) dimers; Versatile pseudohalides; Schiff base; Superstructures; Luminescence;

Thermolysis of [Fe2(CO)6(μ-pdt)] with bis(2-diphenylphosphinoethyl)phenylphosphine (triphos) affords [Fe2(CO)3(μ-pdt){μ,η2-Ph2PCH2CH2P(Ph)CH2CH2PPh2}], the major form of which exists as an interconverting mixture of four isomers at room temperature. Protonation gives a bridging hydride complex in which the fluxionality appears to have been suppressed.Heating [Fe2(CO)6(μ-pdt)] (pdt = SCH2CH2CH2S) and bis(2-diphenylphosphinoethyl) phenylphosphine (triphos) in toluene gives [Fe2(CO)3(μ-pdt){μ,η2-Ph2PCH2CH2P(Ph)CH2CH2PPh2}], the major form of which has been characterised crystallographically. The complex is highly asymmetric; while one iron centre has the expected square-based pyramidal coordination environment, the second is nearer a trigonal bipyramid. In solution at room temperature, four isomers of the major form interconvert via two processes which can be frozen out at low temperature, while protonation affords a bridging hydride complex which appears to be static at all temperatures.
Keywords: Iron-only hydrogenase; Dithiolate; Diiron; Triphos; Fluxionality; Hydride;

An unprecedented bistable monocobalt-benzoquinone complex with six free nitrogen donors has been synthesized and characterized. This compound may apply to the design and synthesis of structural components as a valuable ligand.A novel cobalt-benzoquinone complex containing triethanolaminetriisonicotinate as a coligand, [Co(3,5-dbq)2(tati)2] (3,5-dbq = 3,5-di-tert-butyl-1,2-benzoquinone; tati = triethanolaminetriisonicotinate) is consisted of a valence tautomeric mixture of [CoII] and [CoIII]. The tati coligand acts as a monodentate, resulting in the formation of discrete trans-[Co(3,5-dbq)2(tati)2] with six free nitrogen donors.
Keywords: Bistability; Cobalt complex; Intramolecular electron transfer; Potential hexadentate ligand; Triethanolaminetriisonicotinate;

A novel 2D herringbone-like zinc coordination polymer built from helical motif: Hydrothermal synthesis, structure and properties by Jianguo Lin; Lili Wen; Shuangquan Zang; Yang Su; Zhenda Lu; Huizhen Zhu; Qingjin Meng (74-76).
A novel coordination polymer [Zn(4,4′-bipyridine)(Hptc) · H2O] n (H3ptc = pyridine-2,4,6-tricarboxylic acid) (1) was obtained via hydrothermal method. Single-crystal structural analysis reveals that two kinds (one is left handed and the other is right handed) of parallel helices existed correspondingly, which are connected by rigid 4,4′-bipyridine ligand to give a 2D puckered herringbone structural motif.A novel coordination polymer [Zn(4,4′-bipyridine)(Hptc) · H2O] n (H3ptc=pyridine-2,4,6-tricarboxylic acid) (1) was obtained via hydrothermal method and characterized by elemental analyses, IR spectrum, TG analysis, luminescent spectrum and single-crystal X-ray diffraction analysis. Single-crystal structural analysis reveals that the center Zn2+ions are linked by bridging – carboxylate group of H3ptc, to form helix. The winding axes parallel to the b axis and the pitch to the length is 7.147 Å. Two kinds (one is left handed and the other is right handed) of parallel helices existed correspondingly, which are connected by rigid 4,4′-bipyridine ligand to give a 2D puckered herringbone structural motif.
Keywords: Zinc complex; Crystal structure; Helix; 2D herringbone structure; Luminescence;

A novel lithium salt, cyclobutane-1,1-dicarboxylic lithium was synthesized and characterized by NMR, IR, ESI-MS, X-ray single crystal analysis, and TG/DTG (TGA) thermal analysis. The crystal structure information reveals the coordination polymer nature and ESI-MS shows its aggregation behavior in aqueous solution. TGA analysis discloses the CO2 release with respect to temperature rise.A novel lithium salt, cyclobutane-1,1-dicarboxylic lithium was synthesized and characterized by NMR, IR, ESI-MS, X-ray single crystal analysis, and TG/DTG (TGA) thermal analysis. The crystal structure information reveals the coordination polymer nature and ESI-MS shows its aggregation behavior in aqueous solution. TGA analysis discloses the CO2 release with respect to temperature rise.
Keywords: Coordination polymer; Lithium salt; Crystal structure; TGA analysis;

Cost efficient synthesis of bismuth aminoalkoxides from bismuth oxide: Molecular structure of [Bi2(mdea)2(mdeaH)2](mdeaH2)2 by Jérome Le Bris; Liliane G. Hubert-Pfalzgraf; Stéphane Daniele; Jacqueline Vaissermann (80-83).
Bismuth(III) aminoalkoxides were prepared directly from the reaction between bismuth oxide with N-methyldiethanolamine (mdeaH2) and triethanolamine (teaH3) in refluxing toluene. The compounds are free of inorganic counterions, making them potentially useful as metal–organic precursors for thin film oxides.Functional Bi alkoxides were prepared by reaction between the oxide and diols such as N-methyldiethanolamine (mdeaH2), diethanolamine (deaH2) and triethanolamine (teaH3) in refluxing toluene in high yields. Similar reactions with polyols without N-donor site lead to oxo species. The derivative obtained with N-methyldiethanolamine was characterised by X-ray diffraction as a dimer [Bi2(mdea)2(mdeaH)2] associated as chains through H-bonding with neutral diol molecules giving the title compound. Bismuth is pseudo 7-coordinate. Bi–O bond distances range from 2.150(5) to 3.093(5) Å with three short ones, whereas the transannular Bi–N bond distances are 2.737 Å av. Thermolysis and hydrolysis reactions are reported.
Keywords: Bismuth; Functional alkoxides; Structure; Sol–gel; Aminoalkoxide; Oxide;

A novel hybrid borate B3O4(OH) · 0.5(C4H10N2) with neutral layered structure, based on the linkages of B–O chains and piperazine ligands, was synthesized under milder hydrothermal conditions. The adjacent layers are stacked in a parallel fashion and further stabilized by hydrogen bonding interactions.A novel hybrid borate B3O4(OH) · 0.5(C4H10N2) 1 was synthesized under milder hydrothermal conditions. The product was characterized by a combination of elemental analysis, FT-IR, thermogravimetric analysis and powder X-ray diffraction, as well as single-crystal X-ray diffraction studies. The structure consists of two types of inorganic borate helices cohered by piperazine rings, giving rise to a neutral hybrid sheet. The adjacent layers are stacked in a parallel fashion and further stabilized by hydrogen bonding interactions.

In this work is shown that the HPLC method for characterising the stereogenic properties of cyclotriphosphazene derivatives containing two equivalent centres of chirality, trans (racemic) and cis (meso) respectively, is more reliable than using 31P NMR spectroscopy on addition of a chiral solvating agent (X = Cl, Ph, PhS, PhNH, PhO).The di-spiro derivatives of the reaction of gem-disubstituted cyclotriphosphazenes, N3P3Cl4X2 (X = Ph, PhS, PhNH, PhO) with 3-amino-1-propanol are expected to exist as cis and trans geometric isomers and exist as meso and racemic, respectively. The geometric isomers were separated by column chromatography on silica gel and analyzed by elemental analysis, mass spectrometry, and 31P and 1H NMR spectroscopies. The stereogenic properties of all the compounds (trans, 2a5a) and (cis, 2b5b) were investigated by 31P NMR spectroscopy on the addition of a chiral solvating agent (CSA), (S)-(+)-2,2,2-trifluoro-1-(9′-anthryl)ethanol; one example of a derivative with the trans configuration (compound 5a, X = PhO) has been found where the 31P NMR/CSA method does not lead to the expected separation of the signals of enantiomers, even up to a molar ratio of CSA:compound of 50:1. On the other hand, chiral HPLC methods have been developed in order to characterize the trans (2a5a) and cis (2b5b) forms of the cyclotriphosphazene derivatives and give good separation of enantiomers for the trans disubstituted compounds (2a5a). It is found that chiral HPLC is more reliable than the 31P NMR/CSA method for characterising the stereogenic properties of the cis and trans isomers of di-spiro 3-amino-1-propanoxy cyclophosphazene derivatives.
Keywords: Cis-1,3-cyclotriphosphazenes; Trans-1,3-cyclotriphosphazenes; Chiral HPLC; NMR; CSA (chiral solvating agent);

Interaction of Ni(acac)2 with 1.5 eq. of [Zr(O i Pr)4( i PrOH)]2 in toluene offers quantitatively less soluble [Zr(O i Pr)3(acac)]2 together with the bimetallic complex NiZr2(acac)(O i Pr)9 (1), displaying high solubility and volatility and possessing unusually high stability in the gas phase.Heterometallic alkoxide complexes possessing a triangular M3(μ-OR)2(μ-OR)3 core are usually highly soluble in organic solvents and often display relatively high stability on transition into gas phase. Each metal atom is connected to four ligands within the core and needs two more donor atoms from the terminal ligands to complete octahedral coordination. This can be achieved for Ni(II), for example, by application of a bidentate chelating ligand such as the acetylacetonate one. Interaction of Ni(acac)2 with 1.5 eq. of [Zr(O i Pr)4( i PrOH)]2 in toluene offers quantitatively [Zr(O i Pr)3(acac)]2 together with the bimetallic complex NiZr2(acac)(O i Pr)9 (1), possessing the desired structure and physical properties.
Keywords: Heterometallic complex; Bimetallic Ni–Zr alkoxide; Polymerization catalysis; Sol–gel; MOCVD;

A novel tetranuclear [Pd422-S2)(H2L1)2] complex, where H2L1 is the anion of 3,5-diacetyl-1,2,4-triazole bis(4-ethylthiosemicarbazone), was synthesized and structurally characterized by single crystal X-ray diffraction. The molecular structure shows an unexpected μ22-S2 bridge, which is shared by all the four palladium atoms. Each trideprotonate 3,5-diacetyl-1,2,4-triazole bis(4-ethylthiosemicarbazone) ligand acts as a hexadentate in a symmetrical manner bridging two metal ions through the two adjacent nitrogen atoms of the central triazole ring. The molecular packing is characterized by hydrogen bond interactions to form a 3D supramolecular architecture with channels running down the c axis in which the lattice water molecules are encapsulated.A novel tetranuclear [Pd422-S2)(H2L1)2] complex, where H2L1 is the anion of 3,5-diacetyl-1,2,4-triazole bis(4-ethylthiosemicarbazone), was synthesized and structurally characterized by single crystal X-ray diffraction. The molecular structure shows an unexpected μ22-S2 bridge, which is shared by all the four palladium atoms. Each trideprotonate 3,5-diacetyl-1,2,4-triazole bis(4-ethylthiosemicarbazone) ligand acts as a hexadentate in a symmetrical manner bridging two metal ions through the two adjacent nitrogen atoms of the central triazole ring. The molecular packing is characterized by hydrogen bond interactions to form a 3D supramolecular architecture with channels running down the c axis in which the lattice water molecules are encapsulated.
Keywords: Bis(thiosemicarbazone); Crystal structure; 1,2,4-triazole; Disulphide-bridged; Tetranuclear palladium(II) complexes; Water molecules encapsulated;

A novel supramolecular adduct formed by CB[6]-based pseudo-rotaxane and hydrated Zn(II) ion by Min Zhao; Zhi-Bin Wang; Yi-Zhi Li; Hui-Lan Chen (101-104).
A novel supramolecular adduct prepared by a pseudo-rotaxane [(H2 C6N2)(CB[6])](NO3)2 and hydrated Zn(II) ion is reported. An infinite 2D network structure of the adduct was formed by the hydrogen bond.A novel supramolecular adduct of [C6N2(CB[6])]3  · [Zn(H2O)6]Cl2  · 14H2O (1) is reported, where C6N2  =  N,N′-bis(2-pyridylmethyl)-1,6-diaminohexane, CB[6] = Cucurbit[6]uril. It consists of a CB[6]-based pseudo-rotaxane and a six-hydrated Zn(II) ion, and forms an infinite 2D network and 3D spatial structure by hydrogen bonding interactions.
Keywords: Pseudo-rotaxane; Cucurbit[6]uril; Supramolecular adduct; Hydrogen bond;

Crystal structure and luminescent properties of new rare earth complexes with a flexible Salen-type ligand by Wei Dou; Jun-Na Yao; Wei-Sheng Liu; Ya-Wen Wang; Jiang-Rong Zheng; Da-Qi Wang (105-108).
A novel Salen-type ligand and its four complexes, [LnL(NO3)3] [Ln = La (1), Nd (2), Eu (3), Tb (4)], were synthesized. The X-ray single-crystal diffraction analysis indicates that the ML type complexes [LaL(NO3)3] and [NdL(NO3)3] are isomorphous. With a proton migration (or transfer) from the phenol function to the imine function, coordination of Ln to the ligand gives the ligand a zwitterionic phenoxo-iminium form. The luminescent property of the Tb(III) complex is described and some factors that influence the luminescent intensity were also discussed.A novel Salen-type ligand and its four complexes, [LnL(NO3)3] [Ln = La (1), Nd (2), Eu (3), Tb (4)], were synthesized. The X-ray single-crystal diffraction analysis indicates that the ML type complexes [LaL(NO3)3] and [NdL(NO3)3] are isomorphous. With a proton migration (or transfer) from the phenol function to the imine function, coordination of Ln to the ligand gives the ligand a zwitterionic phenoxo-iminium form. The luminescent property of the Tb(III) complex is described and some factors that influence the luminescent intensity were also discussed.
Keywords: Synthesis; Complexes; X-ray structure; Luminescent properties;

The synthesis, characterization, crystal structure and magnetic properties of the unique azido-acetato bridged trinuclear triply bridged Cu(II) compound, [Cu3(dpyam)2(μ 1,1N3)2(μ-CH3COO-κ-O 1)2(μ-CH3COO-κ-O 1,O 2)2] · 2(H2O), is reported. In the centrosymmetric compound, the central Cu atom is linked to two terminal Cu atoms by a double acetato bridge and an azido bridge, thereby providing a linear trinuclear unit. The coordination geometry around each of the terminal Cu(II) ions is distorted square pyramidal, while the geometry of the central Cu(II) ion is elongated octahedral. The magnetic susceptibility measurements, measured from 5 to 300 K revealed a weak antiferromagnetic interaction between the Cu(II) ions with a J value of −10.2 cm−1.The synthesis, characterization, crystal structure and magnetic properties of the unique azido-acetato bridged trinuclear triply bridged Cu(II) compound, [Cu3(dpyam)21,1-N3)2(μ-CH3COO-κ-O 1)2(μ-CH3COO-κ-O 1,O 2)2] · 2(H2O), is reported. In the centrosymmetric compound, the central Cu atom is linked to two terminal Cu atoms by a double acetato bridge and an azido bridge, thereby providing a linear trinuclear unit. The coordination geometry around each of the terminal Cu(II) ions is distorted square pyramidal, while the geometry of the central Cu(II) ion is elongated octahedral. The magnetic susceptibility measurements, measured from 5 to 300 K revealed a weak antiferromagnetic interaction between the Cu(II) ions with a J value of −10.2 cm−1. In the EPR no signals for the low-lying doublet are resolved at 77 K.
Keywords: Copper(II); Crystal structure; EPR; Magnetism; Di-2-pyridylamine; Azide bridges;

A 2-D cadmium-centered polymer and its isomers by Jack Y. Lu; Melissa A. Achten; Aiwu Zhang (114-116).
A new two-dimensional coordination polymer, [Cd(NA)2], has been synthesized under hydrothermal reaction conditions. The two-dimensional networks show paired stacking arrangement and the 2-D networks are stabilized via interdigitation and π–π interactions.A new two-dimensional coordination polymer, [Cd(NA)2], has been synthesized under hydrothermal reaction conditions. The two-dimensional networks show paired stacking arrangement and the 2-D networks are stabilized via interdigitation and π–π interactions.
Keywords: Coordination polymer; Two-dimensional structure; Hydrothermal reaction; Nicotinato; Cadmium; Interdigitation;

The metallofulvene or carbene complex RuII(PI)(PCy3)2Cl2 with PI = 3-phenylindeny-lidene and Cy = cyclohexyl shows a longwave-length absorption at λ max  = 490 nm which is attributed to a RuII  →  π carbene MLCT transition. MLCT excitation leads to a reversible release of the carbene ligand which can be intercepted with oxygen. The oxygen adduct (or O-oxide) undergoes a fragmentation which yields CO2 and anthracene.The metallofulvene or carbene complex RuII(PI)(PCy3)2Cl2 with PI = 3-phenylindenylidene and Cy = cyclohexyl shows a long-wavelength absorption at λ max  = 490 nm which is attributed to a RuII  →  π carbene MLCT transition. MLCT excitation leads to a reversible release of the carbene ligand which can be intercepted by oxygen. The oxygen adduct (or O-oxide) undergoes a fragmentation which yields CO2 and anthracene.
Keywords: Electronic spectra; Photochemistry; Ruthenium; Carbene complexes; MLCT; Metallofulvene;

A novel macrobicyclic heterobinuclear Zn(II)–Ni(II) complex with a phenol based dicompartmental ligand possessing contiguous hexa- and pentadentate coordination sites was prepared by a stepwise method.A novel macrobicyclic heterobinuclear Zn(II)–Ni(II) complex with a phenol based dicompartmental ligand possessing contiguous hexa- (N4O2) and pentadentate (N3O2) coordination sites was prepared by a stepwise method. The prepared mono- and bimetallic macrocyclic complexes were characterized by elemental analysis, IR, NMR spectroscopies, and molar conductance measurements. Characterization results confirms the expected C2 symmetric geometry for mononuclear macrocyclic zinc complex. The 1H NMR spectrum and X-ray crystal structure of the macrocyclic Zn(II)–Ni(II) complex demonstrated a C1 symmetric geometry with a five-membered heterocycle ring attached to the diethylenetriamine link as a result of an intramolecular rearrangement. The explanation for these topological transformation and intramolecular rearrangement as well as electrochemical behavior of dinuclear complex are discussed.
Keywords: Dicompartmental ligand; Heterodinuclear complex; Macrobicyclic complex; Zn(II) complex; Ni(II) complex; Diimine link;