Inorganic Chemistry Communications (v.9, #6)

Contents List (iii-ix).

In this paper, we obtained a novel 3d–4f heterometallic coordination polymer by hydrothermal method, which exhibit an interesting two-dimensional topology structure constructed from three-ply-like layers.One novel 3d–4f heterometallic coordination polymer {[ZnPr2(Dinic)4(H2O)8] · H2O} n (1) has been synthesized by hydrothermal method, where Dinic = 2,5-pyridinedicarboxylate. X-ray crystallography reveals that complex 1 possesses an interesting two-dimensional topology structure constructed from three-ply-like layers.
Keywords: Heterometallic complex; 2,5-Pyridinedicarboxylate complex; Hydrothermal reaction; Crystal structure; Three-ply-like layers; Fluorescent properties;

Bioinorganic chemistry of anti-thyroid drugs: An unusual formation of a copper (II) complex by Gouriprasanna Roy; Munirathinam Nethaji; G. Mugesh (571-574).
The first example of a metal complex derived from the anti-thyroid drug Se-methimazole (MSeI) is described. The treatment of the diselenide form of MSeI with copper (II) perchlorate leads to an unexpected deselenation reaction resulting in the formation of a novel copper (II) complex.We report the first example of a metal complex derived from the selenium analogue of the anti-thyroid drug methimazole (MSeI). The treatment of the diselenide form of Se-methimazole with copper (II) perchlorate leads to an unexpected deselenation reaction resulting in the formation of a novel copper (II) complex (7). Theoretical studies are performed on compounds 5 and 6 to understand the structural changes that take place at the imidazole moiety upon deselenation. In addition, glutathione peroxidase (GPx) behavior and lactoperoxidase (LPO) inhibition activities of complex 7 are described.
Keywords: Anti-thyroid drugs; Copper complex; DFT calculations; Lactoperoxidase inhibition activity; Methimazole; Selenium;

Readily prepared polymer-supported molybdenum carbonyls as novel reusable and highly active epoxidation catalysts by Shahram Tangestaninejad; Mohammad Hossein Habibi; Valiollah Mirkhani; Majid Moghadam; Gholamhossein Grivani (575-578).
Molybdenum carbonyl complexes immobilized onto polymer-bound phosphines efficiently catalyze epoxidation of a wide variety of alkenes, including aromatic and aliphatic terminal alkenes using tert-butylhydroperoxide.Molybdenum carbonyl complexes immobilized onto polymer-bound phosphines were easily prepared in two steps from commercially available chloromethylated polystyrene resin. These catalysts were found to efficiently catalyze epoxidation of a wide variety of alkenes, including aromatic and aliphatic terminal alkenes using tert-butylhydroperoxide. The new heterogenized molybdenum carbonyl epoxidation catalysts can be easily recovered by simple filtration and show no appreciable loss of activity even after 10 times of recycling.
Keywords: Heterogeneous catalyst; Molybdenum carbonyl; tert-Butylhydroperoxide; Epoxidation;

Self-assembly and crystal structure of a barium sulfonate chrysin coordination polymer by Zun-Ting Zhang; Juan Shi; Yun He; Ya-Ning Guo (579-581).
A novel barium coordination polymer [Ba(C15H9O7S)2] n was obtained by the self-assembly of Ba(II) with 5,7-bihydroxyflavone-6-sulfonate. The barium(II) atom is in distorted dodecahedron environment of 10 oxygen atoms. The coordination interaction, hydrogen bond and π–π stacking lead to the formation of the 1D chain structural coordination polymer.A novel barium coordination polymer [Ba(C15H9O7S)2] n was obtained by the self-assembly of Ba(II) with a sulfonate derivative of chrysin(5,7-bihydroxyflavone-6-sulfonate). The coordination polymer was characterized by single-crystal X-ray diffraction. Its barium(II) atom is in distorted dodecahedron environment of 10 oxygen atoms. The coordination interaction, hydrogen bond and π–π stacking lead to the formation of a 1D chain structural coordination polymer.
Keywords: Barium coordination polymer; Coordination interaction; Hydrogen bond; π–π stacking;

Chromoionophoric N2S2 macrocycles exhibiting mercury(II) selectivity by Hwan Gyu Lee; Ji-Eun Lee; Kyu Seong Choi (582-585).
Two chromogenic N2S2-donor macrocycles functionalized with p-nitroazobenzene (L 1) and phenyltricyanovinyl (L 2) units were synthesized from an N-phenylated macrocyclic precursor (1) and structurally characterized by single crystal X-ray analyses. Interestingly, L 1 and L 2 exhibited excellent Hg2+ selectivity by showing the drastic metal-induced color change from red to colorless (Δλ max  = 137–140 nm). The sensing ability for Hg2+ with the proposed chromoionophores is due to the stable complexation with 1:1 stoichiometry (metal-to-ligand), which was elucidated by spectrophotometry.Two chromogenic N2S2-donor macrocycles functionalized with p-nitroazobenzene (L 1) and phenyltricyanovinyl (L 2) units were synthesized from an N-phenylated macrocyclic precursor (1) and structurally characterized by single crystal X-ray analyses. Interestingly, L 1 and L 2 exhibited excellent Hg2+ selectivity by showing the drastic metal-induced color change from red to colorless (Δλ max  = 137 − 140 nm). The sensing ability for Hg2+ with the proposed chromoionophores is due to the stable complexation with 1:1 stoichiometry (metal-to-ligand), which was elucidated by spectrophotometry.
Keywords: N2S2-donor macrocycle; Chromoionophore; Hg2+-selective; Spectrophotometry;

A new dansyl derived fluorescent sensor 1 for Cu(II) ions has been isolated, attached to resin and characterized. The fluorescence images of CPG 1000/100 resin with 1 have shown strong fluorescence and complete absence of it in the presence of Cu(II) anions.A new dansyl derived fluorescent sensor for Cu(II) ions (1) has been isolated by four-step organic synthesis with a good yield and characterized by NMR- and ESI-MS methods. UV–Vis and fluorescent titrations of 1 with Cu(II), Co(II), Zn(II), Ni(II), Ca(II) and Mg(II) salts were performed. 1 forms a 1:1 stable complex in solution (1 × 10−6  M) with Cu(II) and does not form such complex with other metals. 1 has been attached to a CPG 1000/100 resin. The fluorescence images of CPG 1000/100 resin with 1 have shown strong fluorescence and complete absence of it in the presence of Cu(II) anions.
Keywords: Fluorescence; Cu(II) sensor; UV–Vis titration; Fluorescent titration; Solid phase synthesis;

Hydrothermal synthesis and structural characterization of a new 2D-layered vanadium diphosphinate: [VO(O2(C6H5)PCH2P(C6H5)O2)] by Ferdinando Costantino; Stefano Midollini; Annabella Orlandini; Lorenzo Sorace (591-594).
A new inorganic–organic hybrid [VO(pcp)], where pcp is the P,P′diphenylmethylenediphosphinate ligand, has been hydrothermally synthesized and structurally characterized. The X-ray analysis revealed an undulated 2D-layered structure, where VO5 moieties are connected through bridging phosphinate groups. Magnetic measurements in the range 300–2 K have shown a weak ferromagnetic interaction between vanadyl groups.A new inorganic–organic hybrid [VO(pcp)], where pcp is the P,P′diphenylmethylenediphosphinate ligand, has been hydrothermally synthesized and structurally characterized. The X-ray analysis revealed an undulated 2D-layered structure, where VO5 moieties are connected through bridging phosphinate groups. Magnetic measurements in the range 300–2 K have shown a weak ferromagnetic interaction between vanadyl groups.
Keywords: Oxovanadium complex; Phosphinate; Hydrothermal synthesis; Hybrid material;

Uranyl pyridine-dicarboxylate compounds with clustered water molecules by Yu-Sheng Jiang; Guang-Hua Li; Ye Tian; Zuo-Lei Liao; Jie-Sheng Chen (595-598).
Two uranyl-containing organic coordination polymers have been prepared through a hydrothermal route and characterized by single-crystal X-ray diffraction, thermogravimetric analyses (TGA) and adsorption measurement 1 possesses infinite water cluster chains, whereas compound 2 exhibits considerable adsorption capacity upon removal of the guest species in the microporous channels.Two uranyl-containing organic coordination polymers, (UO2)2(μ 2-OH)(pdc)2 Zn(bpy)(Ac)2(H2O)9 (1) (H2pdc = pyridine-2,6-dicarboxylic acid, bpy = 4,4′-bipyridine, HAc = acetic acid) and UO2(pdc)(H2O) (2) have been prepared through a hydrothermal route and characterized by single-crystal X-ray diffraction, thermogravimetric analyses (TGA) and adsorption measurement 1 possesses infinite water cluster chains, which play an important role in the stabilization of the crystal structure. Whereas compound 2 is thermally stable up to at least 350 °C, this material exhibits considerable adsorption capacity for water and methanol upon removal of the guest species in the microporous channels.
Keywords: Crystal structure; Water chain; Adsorption; Uranyl compounds;

A new β-octamolybdate-supported compound: [Ni(H2O)(2,2′-bipy)2]2 [β-Mo8O26] · 4H2O · 2CH3COOH was synthesized and structurally characterized by IR, UV spectra, thermogravimetry and differential thermal analysis (TG–DTA) analysis, and X-ray diffraction. In the title compound, the two six-coordinated Ni2+ cations with distorted octahedral configurations are combined by a β-[Mo8O26]4- isopolyanion through two terminal oxygen atoms from the framework of the isopolyanion. It is particularly interesting that the title compound exists in a very “molecular” manner and not as an extended one-dimension chain, two-dimension layer or three-dimension structure unlike many of below-mentioned organic-inorganic compounds containing β-[Mo8O26]4− anion.A new β-octamolybdate-supported compound: [Ni(H2O)(2,2′-bipy)2]2[ β-Mo8O26] · 4H2O · 2CH3COOH was synthesized by reaction of Na2MoO4  · 2H2O, NiCl2  · 6H2O with 2,2′-bipyridine employing a conventional method and structurally characterized by IR, UV spectra, thermogravimetry and differential thermal analysis (TG–DTA) and X-ray diffraction. In the title compound, the two six-coordinated Ni2+ cations with distorted octahedral configurations are combined by a β-[Mo8O26]4− isopolyanion through two terminal oxygen atoms from the framework of the isopolyanion. It is particularly interesting that the title compound exists in a very “molecular” manner and not as an extended one-dimension chain, two-dimension layer or three-dimension structure unlike many of below-mentioned organic–inorganic compounds containing β-[Mo8O26]4− anion.
Keywords: β-Octamolybdate-supported compound; Isopolyanion; Crystal structure;

A 3D novel MOF, Cd3(CTC)2(TED)(H2O)2  · (H3O)2Cl2, was obtained with mixed H3CTC and TED ligands. It is of particular interest that twofold alternate (6,3) nets constructed from Cd centers linking H3CTC ligands are supported by linear TED ligands along the c axis to build the 3D architecture with 7.2 × 8.4 Å2 channels.A novel three-dimensional microporous metal-organic framework (MOF), Cd3(CTC)2(TED)(H2O)2  · (H3O)2Cl2 (1) (H3CTC =  cis,cis-1,3,5-cyclohexanetricarboxylic acid and TED = triethylenediamine), has been synthesized under mild condition with mixed H3CTC and TED ligands. It is of particular interest that twofold alternate (6,3) net subunits constructed from Cd centers and H3CTC ligands are supported by linear TED ligands along the c axis to build a 3D architecture. This structure exhibits about 7.2 × 8.4 Å2 channels along the [100] direction. The water adsorption isotherm shows type I behavior with approximately 0.07 mL/g pore volume. The fluorescent emission spectrum of polymer 1 shows a sharp blue-shift peak at 522 nm (λ ex  = 235 nm).
Keywords: Metal-organic framework; Fluorescence; Crystal structure; cis,cis-1,3,5-Cyclohexanetricarboxylic acid; Triethylenediamine;

A novel 3D diorganotin framework, {[(nBu2Sn)2(dmsa)]2  · MeOH} n (1), has been solvothermally synthesized and structurally characterized by elemental analysis, FT-IR, NMR (1H, 13C, 119Sn) spectra, TGA and X-ray crystallography. The structure analysis of complex 1 reveals that guest methanol molecules are established in the hydrophobic “pseudo-channels” of this framework.A novel 3D diorganotin framework, {[(nBu2Sn)2(dmsa)]2  · MeOH} n (1), has been solvothermally synthesized and structurally characterized by elemental analysis, FT-IR, NMR (1H, 13C, 119Sn) spectra, TGA and X-ray crystallography. The structure analysis of complex 1 reveals that guest methanol molecules are established in the hydrophobic “pseudo-channels” of this framework.
Keywords: meso-2,3-Mercaptosuccinic acid; Organotin; 3D framework; Solvothermal synthesis;

New tin(II) and tin(IV) amidophenolate complexes by Alexandr V. Piskunov; Igor A. Aivaz’yan; Georgii K. Fukin; Evgenii V. Baranov; Andrey S. Shavyrin; Vladimir K. Cherkasov; Gleb A. Abakumov (612-615).
Treatment of tin amalgam with 4,6-di-tert-butyl-N-(2,6-diisopropylphenyl)-o-iminobenzoquinone (imQ) in THF results in formation of bis-(4,6-di-tert-butyl-N-(2,6-diisopropylphenyl)-o-amidophenolato)tin(IV) tetrahydrofuranate (1). The exchange reaction of imQ dilithium derivative with tin dichloride dioxanate in THF solution produces bis-[(4,6-di-tert-butyl-N-(2,6-diisopropylphenyl)-o-amidophenolato)tin(II)] (2). Stannylene (2) reacts with imQ in THF to give 1. Structures of 1 and 2 were determined by X-ray analysis.Treatment of tin amalgam with 4,6-di-tert-butyl-N-(2,6-diisopropylphenyl)-o-iminobenzoquinone (imQ) in THF results in formation of bis-(4,6-di-tert-butyl-N-(2,6-diisopropylphenyl)-o-amidophenolato)tin(IV) tetrahydrofuranate (1). The exchange reaction of imQ dilithium derivative with tin dichloride dioxanate in THF solution produces bis-[(4,6-di-tert-butyl-N-(2,6-diisopropylphenyl)-o-amidophenolato)tin(II)] (2). Stannylene (2) reacts with imQ in THF to give 1. Structures of 1 and 2 were determined by X-ray analysis.
Keywords: o-iminoquinone; Amidophenolate; Stannylene; Tin; X-ray diffraction;

The solid-state structure of bis(4′-(4-pyridyl)-2,2′:6′,2″-terpyridine)ruthenium hexafluorophosphate nitrate – An expanded 4,4′-bipyridine by Edwin C. Constable; Catherine E. Housecroft; Markus Neuburger; Silvia Schaffner; Frank Schaper (616-619).
A convenient synthesis of 4′-(4-pyridyl)-2,2′:6′,2″-terpyridine (2) is presented along with the preparation, spectroscopic and structural characterisation of [Ru(2)2][PF6][NO3] · DMSO containing the metallotecton [Ru(2)2]2+.A convenient synthesis of the ligand 4′-(4-pyridyl)-2,2′:6′,2″-terpyridine (2) is presented and the preparation, spectroscopic and structural characterisation of [Ru(2)2][PF6][NO3] · DMSO containing the metallotecton [Ru(2)2]2+ is reported.
Keywords: Ruthenium(II); X-ray; 2,2′:6′,2″-terpyridine; Synthesis;

High efficient polymer light-emitting diode based on a new iridium(III) complex with pyrazolone ligand by Li Shen; Zhao Chen; Qiang Zhao; Fu-You Li; Tao Yi; Yong Cao; Chun-Hui Huang (620-623).
A new iridium complex with 1,3-diphenyl-4-phenylacetyl-5-pyrazolone was synthesized, and its photophysical, electrochemical and electrophosphorescence properties were investigated. By using the complex as dopant, a saturated red polymer-based electrophosphorescent device with high external quantum efficiency of 8.5% was successfully fabricated.A new iridium complex containing two 2-(thiophen-2-yl)quinoline ligands and one single monoanionic ligand 1,3-diphenyl-4-phenylacetyl-5-pyrazolone was designed and synthesized. Its photophysical, electrochemical and electrophosphorescence properties were investigated. The iridium complex in solution showed characteristic phosphorescence with a high quantum efficiency of 19% and lifetime of 0.67 μs. Importantly, a saturated red polymer-based electrophosphorescent device with high external quantum efficiency of 8.5% and CIE coordinate of (0.64, 0.33) was fabricated by using this complex as dopant.
Keywords: Iridium complex; Pyrazolone; Electrophosphorescence; polymer light-emitting diode;

A new structure type of layered fluorinated indium phosphate with In/P ratio of 1/2 [C4N2H12]2[In3(HPO4)5(H2PO4)F2] (1), has been hydrothermally synthesized. It is the first 2-D fluorinated indium phosphate comprising of double-sheet layers with 8-ring channels and diprotonated piperazine cations.A new structure type of layered fluorinated indium phosphate with In/P ratio of 1/2, [C4N2H12]2[In3(HPO4)5(H2PO4)F2] (1), has been hydrothermally synthesized in the presence of piperazine as the structure directing agent. Its structure is built up from In-centered octahedra (InO4F2 and InO5F) and P-centered tetrahedra (PO3(OH), PO2(OH)(=O) and PO(OH)2(=O)), forming the unique double-sheet inorganic layers with 8-ring channels along the [0 1 0] directions.
Keywords: Fluorinated indium phosphate; Hydrothermal synthesis; Double-sheet layer; 8-ring channel;

Nanodimensional pores of zeolite-Y containing; 1,9-dialkyl-1,3,7,9,11,15-hexaazacyclohexadecane, [Cu(R2[16]aneN6)]2+ (R = Me, Et, Bu and Benzyl); have been prepared by the in situ one-pot template synthesis of formaldehyde and 1,3-propylenediamine (1,3-pn) with alkyl and benzyl amine within the nanodimensional pores of zeolite-Y. The host–guest nanocomposite materials catalyze the oxidation of tetrahydrofuran with hydrogen peroxide.Nanodimensional pores of zeolite-Y containing; 1,9-dialkyl-1,3,7,9,11,15-hexaazacyclohexadecane, [Cu(R2[16]aneN6)]2+ (R = Me, Et, Bu and Benzyl); have been prepared by the in situ one-pot template synthesis of formaldehyde and 1,3-propylenediamine (1,3-pn) with alkyl and benzyl amine within the nanodimensional pores of zeolite-Y. The host–guest nanocomposite materials catalyze the oxidation of tetrahydrofuran with hydrogen peroxide.
Keywords: Nanocomposite; Copper(II); 16-Membered macrocycle; Hexaaza; Oxidation;

A new rare-earth metal acylpyrazolonate containing the Zundel ion H 5 O 2 + stabilized by strong hydrogen bonding by Claudio Pettinari; Fabio Marchetti; Riccardo Pettinari; Andrey Drozdov; Sergey Semenov; Sergey I. Troyanov; Vladislav Zolin (634-637).
A new luminescent europium derivative [H5O2][Eu(L)4] characterized by high thermal stability, ionic in acetone and ethanol solution, contains the Zundel cations H 5 O 2 + stabilized by strong hydrogen bonding with the N atoms of the anionic heterocyclic ligand L.A new luminescent europium derivative [H5O2][Eu(QCy)4] (1) (HQCy  = 1-phenyl-3-methyl-4-cyclohexanecarbonylpyrazole-5-one), achievable in high yield, characterized by high thermal stability, ionic in acetone and ethanol solution, contains the Zundel cations H 5 O 2 + stabilized by strong hydrogen bonding with the N atoms of the anionic heterocyclic ligand (QCy).
Keywords: Lanthanide; Pyrazolones; Luminescent; Acid complex; Structure; Zundel cation;

A rare mixed-valence state manganese(II/IV) tetranuclear cage formed using phenyl 2-pyridyl ketone oxime and azide as ligands by Constantinos J. Milios; Stergios Piligkos; Aidan R. Bell; Rebecca H. Laye; Simon J. Teat; Ramon Vicente; Eric McInnes; Albert Escuer; Spyros P. Perlepes; Richard E.P. Winpenny (638-641).
The use of a reaction “blend” containing MnII, PhCO 2 - , phenyl 2-pyridyl ketone oxime and N 3 - leads to a new tetranuclear cage featuring the unprecedented [ Mn 3 II Mn IV ( μ 4 - O ) ( η 1 , μ 2 - N 3 ) ] 7 + core with a 2 e difference between the manganese oxidation states.The reaction of Mn(O2CPh)2  · 2H2O with the sodium salt of phenyl 2-pyridyl ketone oxime and sodium azide in MeOH gives a tetranuclear cage with a [ Mn 3 II Mn IV ( μ 4 - O ) ( η 1 , μ 2 - N 3 ) ] 7 + core. Magnetic and EPR studies show the cage has an S  = 6 ground state.
Keywords: Cages; End-on azide ligands; EPR spectra; Magnetic properties; Mixed-valence manganese complex; Phenyl 2-pyridyl ketone oxime metal complexes;

The inhibition of xanthine oxidase by the Schiff base zinc(II) complex by Zhong-Lu You; Da-Hua Shi; Hai-Liang Zhu (642-644).
A Schiff base zinc(II) complex was synthesized and evaluated for the first time for its effect on the xanthine oxidase (XO). The complex had higher XO inhibitory activity than those of the corresponding Schiff base ligand and the metal ion used in the preparation of the complex, and even more effective than the standard inhibitor allopurinol.A dinuclear Schiff base zinc(II) complex was synthesized, characterized and evaluated for the first time for its effect on the xanthine oxidase (XO). The complex showed higher XO inhibitory activity than those of the corresponding Schiff base ligand and the metal ion used in the preparation of the complex, and even more effective than the standard inhibitor allopurinol.
Keywords: Schiff base; Zinc complex; Xanthine oxidase; Inhibition;

A 2D network complex [Ag2(pydco)] n (1) (pydco = pyridine-2,6-dicarboxylic acid N-oxide) was synthesized and structurally characterized, which contains infinite 1D silver strings via Ag–Ag contacts. Fluorescence spectrum of complex 1 and the free ligand in the solid state at room temperature indicates that the cooperative association of Ag–Ag contacts and the intraligand (π–π) interactions lead to the unusual intense fluorescent emission upon photoexcitation.A 2D network complex [Ag2(pydco)] n (1) (pydco = pyridine-2,6-dicarboxylic acid N-oxide) was synthesized and structurally characterized. Fluorescence spectrum of complex 1 and the free ligand indicates that the cooperative association of Ag–Ag contacts and the intraligand (π–π) interactions lead to the unusual intense fluorescent emission upon photoexcitation.
Keywords: Coordination polymer; Ag–Ag contacts; Silver strings; Fluorescence spectrum; X-ray structure;

Two new mixed-ligand supermolecular polymers of Pr(III) and Ho(III) have been synthesized. The results of single-crystal X-ray diffraction reveal that they crystallize isomorphously in the monoclinic space group P2(1)/n and consist of one-dimensional ribbons featuring dinuclear units. The one-dimensional ribbons are assembled into two-dimensional networks by strong π–π stacking interactions with a distance of ca. 3.31 Å for 1 and ca. 3.27 Å for2. Their liquid-phase formation enthalpy changes were determined in DMF solvent at 25.15 °C using an RD496-III type microcalorimeter.Two novel one-dimensional ribbon-like mixed-ligand supermolecular polymers, [Ln(5-nip)(phen)(NO3) (DMF)] n (Ln = Pr (1) and Ho (2)), assembled into two-dimensional networks by strong π–π stacking interactions, have been synthesized by reactions of lanthanide (III) salts with 5-nitroisophatha acid (5-H2nip) and 1,10-phenanthroline (phen) in DMF solvent. They possessed high thermal stabilities and their liquid-phase formation enthalpy changes were determined in DMF solvent at 25.15 °C using an RD496-III type microcalorimeter, which were Δ r H m θ ( 1 ) = − 9.21 kJ mol − 1 , and Δ r H m θ ( 2 ) = − 11.02 kJ mol − 1 , respectively.
Keywords: Praseodymium; Holmium; 5-Nitroisophatha acid; 1,10-Phenanthroline; Supermolecular polymers;

Efficient transesterification by polymer-supported zinc complexes: Clean and recyclable catalysts by Dong-Woo Yoo; Jung-Hee Han; Sang Ho Nam; Hee Jin Kim; Cheal Kim; Jin-Kyu Lee (654-657).
Polymer-supported Zn catalysts showed an efficient heterogeneous catalytic activity with an easy recyclability on the transesterification under the mild conditions.Polymer-supported Zn catalysts for the transesterification were successfully prepared by deliberately choosing the polymer surface anchored AMP (2-aminomethylpyridine) as a ligand and they showed a heterogeneous catalytic activity with an easy recyclability on the transesterification reaction of various substrates by methanol at room temperature under the mild and neutral conditions.
Keywords: Polymer-supported catalysts; Zn catalysts; Transesterification; Heterogeneous catalysts; Recyclable;

Stereoselective cyclopalladation of [(N-methyl-N-aryl)amino]methylferrocenes 1af (aryl = 4-CH3OC6H4(a), 4-CH3C6H4(b), C6H5(c), 4-ClC6H4(d), 3-ClC6H4(e), 3-O2NC6H4(f)) with sodium palladium tetrachloride and followed by treatment with triphenylphosphine resulted in the cyclopalladated complexes 3af (aryl = same as before) in the form of raceme. The structure of 3a was determined by X-ray single crystal diffraction. Complex 3a crystallizes in triclinic, space group P-1 with a  = 10.6685(14), b  = 10.7412(14), c  = 16.795(2)Å, α  = 71.879(2), β  = 85.798(2), γ  = 64.523(2)°. The possible mechanism for the formation of 3 was discussed.Stereoselective cyclopalladation of [(N-methyl-N-aryl)amino]methylferrocenes 1af (aryl = 4-CH3OC6H4(a), 4-CH3C6H4(b), C6H5(c), 4-ClC6H4(d), 3-ClC6H4(e), 3-O2NC6H4(f)) with sodium palladium tetrachloride and followed by treatment with triphenylphosphine resulted in the cyclopalladated complexes 3af (aryl = same as before) in the form of raceme. The structure of 3a was determined by X-ray single crystal diffraction. Complex 3a crystallizes in triclinic, space group P-1 with a  = 10.6685(14), b  = 10.7412(14), c  = 16.795(2) Å, α  = 71.879(2), β  = 85.798(2), γ  = 64.523(2)°. The possible mechanism for the formation of 3 was discussed.
Keywords: Ferrocenylamines; Cyclopalladation; Stereoselectivity; Crystal;

Six ferrocenedicarboxylate units with unprecedented coordination modes assembled with four Pb(II) and four Na(I) simultaneously resulting in a novel nano-scale double-wheel-like framework [Pb4Na4(O2CFcCO2)6(H2O)6] · 6CH3OH · 2H2O, whose structure and electrochemical properties were characterized.Six ferrocenedicarboxylate units with unprecedented coordination modes assembled with four Pb(II) and four Na(I) simultaneously resulting in a novel nano-scale double-wheel- like framework [Pb4Na4(O2CFcCO2)6(H2O)6] · 6CH3OH · 2H2O, whose structure and electrochemical properties were characterized.
Keywords: Nano-scale double-wheel-like framework; Ferrocenedicarboxylate; Assembly;