Published Papers - HASHIMOTO Masato

Control over the preference for binding sites of polyoxometalates to silver ethynide clusters by surface charge modification

Sho Tamari, Kosuke Ono, Masato Hashimoto, Tomoji Ozeki

DALTON TRANSACTIONS ( ROYAL SOC CHEMISTRY )  44 ( 44 ) 19056 - 19058   2015  [Refereed]

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A polyoxometalate-silver ethynide composite cluster, [Ag-42(CO3)-{ C = CC(CH3)(3)}(27)(alpha-A-SiW9Nb3O40)(2)](-) (1), demonstrates that we can select the binding site of a polyoxometalate to the silver alkynide cluster by tuning the surface charge of the precursor polyoxometalate. Multidimensional and multinuclear NMR spectra revealed that 1 maintains its precise atomic connectivity in the solution.

DOI

Synthesis, structure and spectroscopic analyses of aquachloridooxidodiperoxidomolybdate(VI)

Masa-aki Saito, Masato Hashimoto

DALTON TRANSACTIONS ( ROYAL SOC CHEMISTRY )  43 ( 2 ) 402 - 405   2014  [Refereed]

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A novel aquachloridooxidodiperoxidomolybdate(VI), [MoClO(O-2)(2)(OH2)](-), was crystallised as tetraethylammonium and triethylmethylammonium salts from strongly acidic aqueous solutions, and was structurally analysed by single crystal X-ray diffraction and NMR spectroscopy. The aqueous behaviour of the present anion observed by O-17 NMR agrees with that reported in a previous speciation study.

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Calcium and strontium salts of (glycinato-κ2 N,O)oxidobis(peroxido-κ2O,O′)vanadate(V) tetrahydrate

Takeshi Higuchi, Ayana Uchida, Masato Hashimoto

Acta Crystallographica Section C: Crystal Structure Communications   69 ( 12 ) 1494 - 1497   2013.12  [Refereed]

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The title salts calcium (glycinato-κ2 N,O) oxidobis(peroxido-κ2 O,O′)vanadate(V) tetrahydrate, Ca[VO(O2)2(NH2CH2COO)] ·4H2O, and strontium (glycinato-κ2 N,O)oxidobis(peroxido-κ2 O,O′)vanadate(V) tetrahydrate, Sr[VO(O2)2(NH2CH2COO)] ·4H2O, crystallized at pH ca 7.4 with similar lattice parameters. The glycinate anion acts as a bidentate N,O-chelating ligand, and the V atom has a pentagonal bipyramidal geometry, with two η2- peroxo groups and the glycinate N atom in the equatorial plane, and one terminal oxo and a glycinate O atom at the axial positions. The H atoms of three of the four water molecules in the strontium salt exhibited disorder over three positions for each molecule. © 2013 International Union of Crystallography.

DOI

Dipotassium Diaquadiphosphatooctaperoxotetramolybdate, [K-2(P2O7){MoO(O-2)(2)}(2){MoO(O-2)(2)(OH2)}(2)](2-) - a One-Dimensional Double Chain Array of Polyanions Linked by Potassium Cations

Koji Aoki, Keisuke Iwata, Takahiro Iwata, Masato Hashimoto

EUROPEAN JOURNAL OF INORGANIC CHEMISTRY ( WILEY-V C H VERLAG GMBH )  ( 10-11 ) 1808 - 1814   2013.04  [Refereed]

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A dipotassium diaquadiphosphatooctaperoxotetramolybdate, [K2(P2O7){MoO(O2)2}2{MoO(O2)2(OH2)}2]2, was crystallised as a tetramethylammonium salt and its structure was determined by single-crystal X-ray diffraction. The diaquadiphosphatooctaperoxotetramolybdate moiety (POPMo4) consists of four molybdenum decahedra and one 4-diphosphate group. All Mo atoms bear two peroxo groups at their equatorial positions. Two of the four Mo atoms are also coordinated by a water molecule. The four molybdenum decahedra are separated and linked by the diphosphate group. The POPMo4 moieties are linked by potassium atoms to form an infinite anionic 1D double chain. The chains are connected by hydrogen bonds to water of crystallisation molecules to form a 2D network. POPMo4 or its precursor gives a 31P NMR signal at = 7.3 ppm in the reaction solution and is stable at low pH and a high Mo/diphosphate molar ratio.

DOI

Potassium, rubidium and ammonium salts of -(formato-2O:O)--oxido-bis[oxidobis(peroxido-2O,O)molybdate(VI)]

Masaki Takehara, Masato Hashimoto

ACTA CRYSTALLOGRAPHICA SECTION C-CRYSTAL STRUCTURE COMMUNICATIONS ( WILEY-BLACKWELL )  69   37 - +   2013.01  [Refereed]

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The unit-cell parameters of the three title salts, namely, tripotassium, K3[Mo2(CHO2)O3(O2)4], trirubidium, Rb3[Mo2(CHO2)O3(O2)4], and triammonium -(formato-2O:O)--oxido-bis[oxidobis(peroxido-2O,O)molybdate(VI)], (NH4)3[Mo2(CHO2)O3(O2)4], which were all crystallized at pH 3, are quite similar, but the potassium and rubidium salt structures are noncentrosymmetric, whereas that of the ammonium salt is centrosymmetric. Formate acts as an O:O-bridging ligand in the complex anion and is bound to a -oxido-bis(oxidodiperoxidomolybdate) unit.

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Bis(trimethylphenylammonium) μ-oxalato-bis[oxidodiperoxidomolybdate(VI)]

Ayaka Oba, Masato Hashimoto

Acta Crystallographica Section E: Structure Reports Online   68 ( 12 ) m1467   2012.12  [Refereed]

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A trimethylphenylammonium salt of a dinuclear μ-oxalate complex of diperoxidomonomolybdate units, (C9H14N)2[Mo2(C2O4)(O2)4O2], was obtained from an acidic aqueous solution
the dianion is located about a centre of inversion. Each Mo atom bears two peroxide groups together with one O atom from the oxalate group in its equatorial positions and one terminal O atom as well as another O atom from the oxalate in axial positions. The oxalate group acts as a tetradentate bridging ligand and bridges between the diperoxidomolybdate units.

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Role of p(Z)-pi(Ar/Nap) conjugation in structures of 1-(arylchalcogena)-naphthalenes for Z = Te versus Se, S and O: experimental and theoretical investigations

Takahito Nakai, Mitsuhiro Nishino, Satoko Hayashi, Masato Hashimoto, Waro Nakanishi

DALTON TRANSACTIONS ( ROYAL SOC CHEMISTRY )  41 ( 25 ) 7485 - 7497   2012  [Refereed]

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Magnitudes of the p(Z)-pi(Ar/Nap) conjugation were evaluated for 1-(arylchalcogena)naphthalenes (1-(ArZ)Nap, 1-(p-YC(6)H(4)Z)C10H7; 1 (Z = Te), 2 (Se), 3 (S) and 4 (O)). Structures of 1 were determined by X-ray analysis for Y = NMe2 (b), OMe (c) and CN (i). For 1b and 1c that have electron donating Y, the Z-C-Ar bond is located on the naphthyl plane with Z-C-Nap being perpendicular to the aryl plane, which we define as (B: pd). On the other hand, the structure of 1i with electron donating Y is (A: pl), of which Z-C-Ar is placed almost perpendicular to the naphthyl plane with Z-C-Nap being located on the aryl plane. Each structure of 1a (Y = H), 1b, 1c, 1d (Me), 1e (F), 1f (Cl), 1g (Br), 1h (COOEt), 1i and 1j (NO2) was determined by NMR in chloroform-d. Structures of 1 in the solutions are (B: pd) for b, c and e that have electron donating Y, (A: pl) for f-j with electron accepting Y, and in equilibrium between (B: pd) and (A: pl) for a and d of which Yare rather neutral. The results for 2-4 are very similar to those of 1 in solutions. Quantum chemical calculations were performed on 1-4 with Yof a, b' (NH2), d, f and j. Magnitudes of the p(Z)-pi(Ar/Nap) conjugation were well-evaluated by NBO (natural bond orbital) analysis. The values were 12.6 and 13.0 kcal mol(-1) for the typical forms of (A: pl) and (B: pd) of 1a, respectively, resulting in a much smaller energy difference between the two (0.4 kcal mol(-1)), which should correspond to the observed result. It is well-demonstrated that the p(Te)-p(Ar/Nap) conjugation operates effectively in 1, although the magnitudes increase in the order of Z = Te < Se < S < O. Thermal effect of the Gibbs free energies is shown to play an important role in the energy profiles of 1a-4a.

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A P-31-NMR study of the H+-MoO42--(HP)O-3(2-)-HPO42--(C6H5P)O-3(2-)-(CH3P)O-3(2-) system at low Mo-tot/P-tot ratio - Formation of mixed-hetero X2M5-type polyanions

Masato Hashimoto, Ingegaerd Andersson, Lage Pettersson

DALTON TRANSACTIONS ( ROYAL SOC CHEMISTRY )  ( 17 ) 3321 - 3327   2009  [Refereed]

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Formation of X2M5-type heteropolyanions in the aqueous mixed-hetero H+-MoO42--(HP)O-3(2-)-HPO42--(C6H5P)O-3(2-)- (C6H3P)O-3(2-) system has been studied by P-31-NMR at [Mo](tot)/[P-all](tot) = 1.5 at 298(1) K in 0.600 M Na(Cl) ionic medium. The -log[H+] range 1.4-6.2 has been covered. The pK(a) values of methylphosphonate were determined from P-31-NMR chemical shift data in the range of 0 < -log[H+] < 13.2 as H(CH3P)O-3(-) 7.30 and H-2(CH3P)O-3 2.05. All four-component H+-MoO42--P1-P2 subsystems (P1 and P2 are two of the four phosphorus-containing components), except H+-MoO(4)2(-)-(HP)O-3(2-)-HPO42-, which has been studied previously, were examined instead of the full six-component system in order to simplify the evaluation of the NMR spectra. The concentrations were adjusted to [Mo](tot) = 60 mM and [P1](tot) = [P2](tot) = 20 mM in the measurements. All conceivable P2M5 and (P1)(P2)M5 heteropolyanions were identified. The following novel X2M5-type polyanions were found and their formation constants are given in logarithmic values with 36 in parentheses: (CH3P)(2)Mo5O214- 69.68(7), (HP)(C6HSP)Mo5O214- 67.09(4), (C6H5P)PMo5O225- 63.23(5), H(C6H5P)PMo5O224- 68.11(4), (HP)(CH3P)Mo5O214-- 67.85(4), (CH3P)PMo5O225- 64.14(7), H(CH3P)Mo5O224- 68.89(4) and (C6H5P)(CH3P)Mo5O214- 69.18(4). The equilibrium conditions are illustrated in distribution diagrams. Phosphite proved to bind more weakly in X2M5-type polyoxometallates than phosphate or phosphonates, which are almost equally favoured in complexation.

DOI

Preparation and Characterization of an alpha-Wells-Dawson-Type [V2Mo18O62](6-) Complex

Sadayuki Himeno, Keishi Kawasaki, Masato Hashimoto

BULLETIN OF THE CHEMICAL SOCIETY OF JAPAN ( CHEMICAL SOC JAPAN )  81 ( 11 ) 1465 - 1471   2008.11  [Refereed]

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An orange-yellow vanadomolybdate complex was prepared by heating a 100 mM Mo-VI-20 mM V-V-0.45 M HCl-20% (v/v) CH3CN system at 70 degrees C for 24 h, being isolated as the tetrapropylammonium (Pr4N+) salt. The Pr4N+ salt crystallized in the orthorhombic space group P2(1)2(1)2; the lattice constants were a = 18.417(4), b = 20.869(5), c = 15.280(3) angstrom, V = 5873(2) angstrom(3), and Z = 2. The crystallographic study revealed that the structure consists of The alpha-Wells-Dawson-type [V2Mo18O62](6-) anion, in which vanadates serve as the central tetrahedra. alpha-[V2Mo18O62](6-) complex underwent a two-step one-electron reduction in CH3CN, and the presence of acid caused the one-electron waves to be converted into three two-electron waves. The formation conditions were elucidated by V-51 NMR measurements.

DOI

An equilibrium analysis of the aqueous H+-MoO42--(HP)O-3(2-)-H+MoO42--(HP)O-3(2-)-(HPO)(4)(2-) and systems

Masato Hashimoto, Ingegaerd Andersson, Lage Pettersson

DALTON TRANSACTIONS ( ROYAL SOC CHEMISTRY )  ( 1 ) 124 - 132   2007.01  [Refereed]

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The speciation in the phosphitomolybdate system, H+-MoO42--(HP)O-3(2-), has been determined from combined potentiometric and P-31 NMR measurements in 0.600 M Na(Cl) medium at 298(1) K. Potentiometric titration data were collected in the ranges 2.5 < -log[H+] < 6.2, 40.0 <= [Mo](tot) <= 240.0 mM, 10.0 <= [P](tot) <= 40.0 mM and l <= [Mo](tot)/[P](tot) <= 10. P-31 NMR data were collected in the same ranges with the exception that -log[H+] was decreased to 0.8. The pK(a) values of phosphite were determined by means of potentiometric (1.5 < -log[H+] < 8.6) and P-31 NMR chemical shift data (0.0 < -log[H+] < 12.0). The following log beta (3 sigma) values were deduced: H(HP)O-3(-), 6.09(2); H-2(HP)O-3, 7.23(4) (pK(a) = 1. 14). In the phosphitomolybdate system, the following complexes were found along with their formation constants ((HP) denotes phosphite): Mo-5(HP)(2)(4-), 65.31(4); Mo-6(HP)(2)(5-), 71.94(5); Mo-5(HP)(4-), 51.25(8); Mo-5(HP)(3-), 54.9(3); Mo-6(HP)(2-), 68.99(9); Mo-7(Hp)(5-), 71.25(3); Mo-7(HP)(4-), 74.2(2). Because hydrolysis and oxidation of phosphite to phosphate were observed by NMR, with a mixed-hetero species of low [Mo](tot)/[P](tot) ratio being detected, the four-component H+-MoO42-(HP)-O-3(2-)-HPO42- system was also studied in the same way over the range 0.8 < -log[H+] < 6.2 and [Mo](tot)/[P](tot) fixed at 1.5. The following mixed heteropolyanion species have been found (P denotes the phosphate group): Mo-5(HP)P5-, 62.27(6); Mo-5(HP)P4-, 66.76(4). The equilibrium speciation in the two systems are illustrated by distribution diagrams. In addition, the aqueous structures are proposed for all the species formed in the systems.

DOI

Preparation, structure, and characterization of a novel diphosphoheptadecatungstate complex, [(P2O7)W17O51](4-)

S Himeno, T Katsuta, M Takamoto, M Hashimoto

BULLETIN OF THE CHEMICAL SOCIETY OF JAPAN ( CHEMICAL SOC JAPAN )  79 ( 1 ) 100 - 105   2006.01  [Refereed]

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A novel diphosphoheptadecatungstate complex, [(P2O7)W17O51](4-) was prepared from a 200 mM (M = mol dm(-3)) W(VI)-10 mM P2O74--0.6 M HCl-40% (v/v) CH3CN system, and characterized by IR, UV-vis, P-31 NMR, and W-183 NMR spectroscopy, and voltammetry. Single-crystal X-ray analysis was made on [(C2H5)(4)N](4)[(P2O7)W17O51]center dot CH3CN, which crystallized in the monoclinic space group P2(1)/n, with cell parameters a = 16.1877(8), b = 22.103(1), c = 21670(1) angstrom, beta = 90.847(1)degrees, V = 8110.3(7) angstrom(3), and Z = 4. The anion consists of a PW8O31 fragment derived from a beta-Keggin-type [PW12O40](3-) structure, and two PW8O31 units are linked by five oxygen atoms and a WO5 square pyramid. The [(P2O7)W17O51](4-) anion exhibited a four-step reversible one-electron redox wave in CH3CN, and a three-step two-electron redox wave resulted in the presence of acid. This is the first example of an electrochemically-active diphosphotungstate complex.

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First transition metal complex of 1,8-bis(dimethylamino)naphthalene (proton sponge)

T Yamasaki, N Ozaki, Y Saika, K Ohta, K Goboh, F Nakamura, M Hashimoto, S Okeya

CHEMISTRY LETTERS ( CHEMICAL SOC JAPAN )  33 ( 7 ) 928 - 929   2004.07  [Refereed]

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First transition metal complexes of 1,8-bis(dimethyl-amino)naphthalene (proton sponge), N,N'-chelated Pd(II) complexes, were prepared and the strong coordination ability of the proton sponge was demonstrated. The high transition energy for the coordination could be lowered by the existence of the intermediate charge-transfer complex which was isolated.

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Preparation and characterization of an alpha-Keggin-type [SW12O40](2)-complex

S Himeno, M Takamoto, M Hoshiba, A Higuchi, M Hashimoto

BULLETIN OF THE CHEMICAL SOCIETY OF JAPAN ( CHEMICAL SOC JAPAN )  77 ( 3 ) 519 - 524   2004.03  [Refereed]

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A divanadium-substituted derivative of 12-tungstosulfate(VI), [S(V2W10)O-40](4-) was prepared as the tetrabutylammonium (n-Bu4N+) salt by heating a 50 nM (M = mol dm(-3)) W(VI)-20 mM V(V)-0.5 M H2SO4-50% (v/v) CH3CN system at 70 degreesC for 24 h. The [S(V2W10)O-40](4-) anion Was transformed spontaneously into a monovanadium-substituted derivative, [S(VW11)O-40](3-) in a 70% (v/v) CH3CN-1.0 M HCl system at 70 degreesC. Oil the other hand, [SW12O40](2-) was precipitated as the n-Bu4N+ salt upon heating a 95% (v/v) CH3CN-0.5 M HCl system containing [S(V2W10)O-40](4-). The single-crystal X-ray structural analysis revealed that the structure consisted of an alpha-Keggin-type [SW12O40](2-) anion. The [SW12O40](2-) anion was characterized by IR and UV-vis spectroscopy, and voltammetry.

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Synthesis and Crystal Structure of Cs₂(CN₃H₆)₃[(C₂H₅)₂NH₂][W₇O₂₂(O₂)₂].3H₂O

Hiroyuki Suzuki, Masato Hashimoto, Seichi Okeya

Eur. J. Inorg. Chem.     2632 - 2634   2004  [Refereed]

Synthesis and structural characterization of [HxCp*TiMo5O18]((3-x)-) (x=0, 1, 2); new insights into protonation patterns in polyoxometalates

H Akashi, J Chen, H Hasegawa, M Hashimoto, T Hashimoto, T Sakuraba, A Yagasaki

POLYHEDRON ( PERGAMON-ELSEVIER SCIENCE LTD )  22 ( 20 ) 2847 - 2854   2003.09  [Refereed]

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Reaction Of [(n-C4H9)(4)N](2)[Mo2O7], Cp*TiCl3, and [(n-C4H9)(4)N]OH in CH3CN yields [(n-C4H9)(4)N](3)[Cp*TiMo5O18].CH3CN [a = 12.863(4) Angstrom b = 26.608(6) Angstrom, c = 24.534(4) Angstrom, beta = 103.88(2)degrees, Z = 4, space group P2(1)/c (no. 14)]. Similar reaction without [(n-C4H9)(4)N]OH yields monoprotonated complex [(n-C4H9)(4)N](2)[HCp*TiMo5O18], where, according to a single-crystal X-ray diffraction study [a = 19.9550(4) Angstrom, b = 25.5420(8) Angstrom, c = 11.8820(3) Angstrom, beta = 100.31(2)degrees, Z = 4, space group P2(1)/n (no. 14)], the anion is protonated at one of OMo2 doubly-bridging oxygens. Reaction of [(n-C4H9)(4)N](2)[HCp*TiMo5O18] with CCl3COOH in CHCl3 followed by crystallization from CH3CN/Et2O yields diprotonated [(n-C4H9)(4)N][H2Cp*TiMO5O18].1/4(C2H5)(2)O, which, according to a single-crystal X-ray diffraction study [a = 12.319(2) Angstrom, b = 16.105(3) Angstrom, c = 12.001(2) Angstrom, alpha = 110. 74(1)degrees, beta = 100.31(2)degrees, gamma = 82.777(5) Z = 2, space group P (1) over bar (no. 2)], contains hydrogen-bonded dimers of [H,,Cp*TiMo5O19](-) ions. The [Cp*TiMo5O18](3-) is basic enough to form stable organometallic adducts like [(eta-C8H12)Ir(Cp*TiMo5O18)](2-) and [(eta-C8H14)Rh(Cp*TiMo5O18)](2-). (C) 2003 Elsevier Ltd. All rights reserved.

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O-17 NMR study of aqueous peroxoisopolymolybdate equilibria at lower peroxide/Mo ratios

L Pettersson, Andersson, I, F Taube, Toth, I, M Hashimoto, OW Howarth

DALTON TRANSACTIONS ( ROYAL SOC CHEMISTRY )  ( 1 ) 146 - 152   2003  [Refereed]

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Aqueous peroxomolybdates have been studied using O-17 NMR together with equilibrium measurements and calculations, over a wide range of conditions. Ten peroxo species are identified, mostly in more than one state of protonation. Some are already known in the solid state, or from equilibrium analysis, but structural information is also obtained for MoO3 (HO2)(-) and the new or previously tentative species Mo2O5 (O-2)(2)(2-), HpMo7O23 (O-2)(2)(p-6) and HpMo7O23 (O-2)(p-6) (p = 0-2). Sites of protonation are identified, as are O-17 resonances from both bidentate and monodentate peroxide. Several oxygen exchange processes are also seen, including a probable dimer-tetramer exchange.

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A breathing ionic crystal displaying selective binding of small alcohols and nitriles: K-3[Cr3O(OOCH)(6)(H2O)(3)][alpha-SiW12O40]center dot 16H(2)O

S Uchida, M Hashimoto, N Mizuno

ANGEWANDTE CHEMIE-INTERNATIONAL EDITION ( WILEY-V C H VERLAG GMBH )  41 ( 15 ) 2814 - +   2002  [Refereed]

[Ni(H₂O₆)]₂[Na(H₂O)₃]₂ V₁₀O₂₈・4H₂O

Tomoyuki Higami, Masato Hashimoto, Seichi Okeya

Acta Crystallogr. Sect. C   C58   i144 - i146   2002  [Refereed]

Characterisation of aqueous peroxomolybdate catalysts applicable to pulp bleaching

F Taube, M Hashimoto, Andersson, I, L Pettersson

JOURNAL OF THE CHEMICAL SOCIETY-DALTON TRANSACTIONS ( ROYAL SOC CHEMISTRY )  ( 6 ) 1002 - 1008   2002  [Refereed]

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The equilibrium speciation in the system p H++ q MoO42-+ rH(2)O(2) + sSO(4)(2-) reversible arrow(H+)(p) (MoO42-)(q) (H2O2)(r) (SO42-)s in 0.300 M Na-2 (SO4) medium at 25 degreesC has been determined from potentiometric titration data in the ranges 2.0 less than or equal topH less than or equal to5.5, 5.00 less than or equal to[Mo](tot)/mM less than or equal to80.00, 0 less than or equal to[H2O2](tot)/mM less than or equal to245 and 273.07 less than or equal to[SO42-](tot)/mM less than or equal to320.20. Species with the following compositions were found: MoX- (1,1,1,0), MoX (2,1,1,0), MoX2- (1,1,2,0), MoX2 (2,1,2,0), MoX2S2- (2,1,2,1), Mo2X42- (2,2,4,0), Mo7X6- (8,7,1,0), Mo7X5- (9,7,1,0), Mo7X4- (10,7,1,0) and Mo7X3- (11,7,1,0). The numbers in parentheses refer to the values of p, q, r and s in the formula above. The numbers and charges of molybdenum (Mo), peroxide (X) and sulfate (S) in each species are given in the abbreviated formula MoqXrSs(2q + 2s - p)-. The following formation constants with 3sigma were obtained; logbeta(1,1,1,0) = 8.53 +/- 0.03, log beta(2,1,1,0) = 11.22 +/- 0.04 (pK(a) = 2.69), log beta(1,1,2,0) = 11.61 +/- 0.03, log beta(2,1,2,0) = 13.77 (+/- 0.06) (pK(a) = 2.16), log beta(2,1,2,1) = 14.50 +/- 0.06, log beta(2,2,4,0) = 23.77 +/- 0.11, log beta(8,7,1,0) = 56.71 +/- 0.11, log beta(9,7,1,0) = 62.00 +/- 0.05 (pK(a) = 5.29), log beta(10,7,1,0) = 65.74 +/- 0.06 (pK(a) = 3.74), log beta(11,7,1,0) = 68.23 +/- 0.08 (pK(a) = 2.49). Most complexes have been verified by Mo-95 NMR, O-17 NMR, and the novel MoX2S2- complex also by FTIR spectroscopy.

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Origin of microporosity of ammonium dodecatungstophosphate unveiled by single crystal structure analysis

T Ito, M Hashimoto, S Uchida, N Mizuno

CHEMISTRY LETTERS ( CHEMICAL SOC JAPAN )  ( 12 ) 1272 - 1273   2001.12  [Refereed]

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The single crystals of ammonium dodecatungstophosphate were successfully synthesized and the structure was analyzed. The intrinsic crystal structure (cubic, Pn (3) over barm) had no cavity. It follows that the microporosity observed for the powdery sample originated from narrow spaces surrounded by the fine nanocrystallites.

Synthesis, structure, and characterization of an alpha-Dawson-type [S2W18O62](4-) complex

S Himeno, H Tatewaki, M Hashimoto

BULLETIN OF THE CHEMICAL SOCIETY OF JAPAN ( CHEMICAL SOC JAPAN )  74 ( 9 ) 1623 - 1628   2001.09  [Refereed]

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A yellow sulfatotungstate complex was formed by heating a 50 mM W(Vl)-2 M H2SO4-40% (v/v) CH3CN system at 70 degreesC for 14 days, being isolated as the tetrapropylammonium (n-Pr4N+) salt. An X-ray structural analysis (orthorhombic, Pca2(1) (No. 29) a = 27.181(1), b = 14.1428(6), c = 27.7292(9) Angstrom, and Z = 4) revealed that the structure consists of an alpha -Dawson-type [S2W18O62](4-) anion. The alpha-[S2W18O62](4-) complex underwent a four-step reversible one-electron reduction in CH3CN, and the presence of acid caused the one-electron waves to be converted into three two-electron waves. The formation conditions were elucidated by a combined Raman and voltammetric study.

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A P-31-NMR study of peroxo species formed during oxidation of cyclohexene with hydrogen peroxide in tri-n-butylphosphate catalyzed by heteropolyacids

M Hashimoto, K Itoh, KY Lee, M Misono

TOPICS IN CATALYSIS ( KLUWER ACADEMIC/PLENUM PUBL )  15 ( 2-4 ) 265 - 271   2001  [Refereed]

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In the oxidation of cyclohexene with H2O2 in monophasic tri-n-butylphosphate (TBP) solution catalyzed by Keggin-type 12-heteropolyacids, i.e., H3PMo12-xWxO40 (x = 0-12), several peroxo species were observed by P-31-NMR spectroscopy in lower field than the original heteropolyacids. Their composition varied regularly with that of the starting catalyst. The P-containing peroxo species formed was deduced as [PM4O8(O-2)(8)](3-) (M = Mo, W). The peroxo species formed more easily with a decrease in the W content, x of H3PMo12-xWxO40. It was further indicated from the reactivity with cyclohexene and the comparison with catalytic performance that W-rich peroxo species were catalytically more active than Mo-rich peroxo species for the oxidation of cyclohexene in this reaction system.

Facile formation and dissociation behaviour of C-C bond resulted from the nucleophilic attack of carbanions on a carbonyl carbon in [Pt(hfac)(2)]

S Okeya, M Hashimoto, F Nakamura, Y Kusuyama, M Kobayashi, R Arakawa

CHEMISTRY LETTERS ( CHEMICAL SOC JAPAN )  ( 10 ) 1130 - 1131   2000.10  [Refereed]

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[Pt(hfac)(2)] (hfac: hexafluoroacetylacetonate) reacts with MeNH2 in CH2Cl2/MeOH to give an -NHMe adduct complex on one of the carbonyl carbons, (MeNH3) [Pt(hfac)(hfac-NHMe)] 1 which is a tetrahedral intermediate of a Schiff base complex, [Pt(CF3COCHC(NMe)CF3)(2)] 2. Complex 1 activates H2O, MeOH, MeNO2 or acetone in solution to form the corresponding conjugate base adducts. The C-C bond in -CH2NO2 adduct 6, easily cleaves and generates nitromethane in solution.

Reactivity of organometallic molybdate toward lanthanide cations. Synthesis and structure of polynuclear lanthanide-molybdate complexes

M Hashimoto, M Takata, A Yagasaki

INORGANIC CHEMISTRY ( AMER CHEMICAL SOC )  39 ( 16 ) 3712 - +   2000.08  [Refereed]

　View Summary

Novel polynuclear rare earth compounds [La-3(OH2)(7)-(Cp*MoO3)(2)(NO3)(7)] and [La-3(OH2)(5)(THF)(Cp*MoO3)(2)-(NO3)(6)](2)(NO3)(2) were synthesized by reacting [(n-C4H9)(4)N][CP*MoO3] With La(NO3)(3). 6H(2)O in THF. X-ray crystal structural analyses revealed that both these compounds are composed of a La3Mo2O6 unit in which the metal atoms arrange themselves into a trigonal bipyramid. The Ce analogues were also obtained.
[GRAPHICS]

DOI

[NH₄]₃[VO₂(SO₄)₂(OH₂)₂].1.5H₂O

Masato Hashimoto, Michiru Kubata, Atsushi Yagasaki

Acta Crystallogr., Sect. C   C56   1411 - 1412   2000  [Refereed]

Multicomponent polyanions. 52. Crystal structure of hexacaesium monohydrogen decamolybdo(VI)divanado(IV)phosphate(7-) dihydrate

M Hashimoto, A Selling, M Hakansson, L Pettersson

ACTA CHEMICA SCANDINAVICA ( MUNKSGAARD INT PUBL LTD )  53 ( 5 ) 305 - 313   1999.05  [Refereed]

　View Summary

The structure of the title compound, (Cs6HPMo10V2O40)-V-VI-O-IV. 2H(2)O has been determined by a single-crystal X-ray diffraction method. The compound crystallises in two different space groups. Crystal A: monoclinic P2(1), a = 10.988(3), b = 10.615(3), c = 17.472(2) Angstrom, beta = 91.55(1)degrees, V = 2037(7) Angstrom(3) and Z = 2. Crystal B: monoclinic, Pn, a = 10.982(2), b = 10.614(3), c = 17.487(3) Angstrom, beta = 91.64(1)degrees, V = 2037(7) Angstrom(3) and Z = 2. The R-values based on F were 0.0487 for A and 0.0485 for B for 4491 (A) and 4464 (B) reflections with F-o > 4.0 sigma (F-o) and 353 parameters, and S = 1.048 (A) and 1.026 (B). The polyanion has a so-called alpha-Keggin structure in each crystal. The two vanadium atoms are delocalised in the 12 addenda atom positions in the anion.

Formation and conversion of molybdophosphate and -arsenate complexes in aqueous solution

S Himeno, M Hashimoto, T Ueda

INORGANICA CHIMICA ACTA ( ELSEVIER SCIENCE SA )  284 ( 2 ) 237 - 245   1999.01  [Refereed]

　View Summary

The difference between the formation and conversion processes of molybdophosphate and -arsenate complexes was elucidated in a 100 mM Mo(VI)-0.5 M HCl system as a function of the P(V) or As(V) concentration. In the Mo(VI)-P(V) system, the Keggin-type [PMo12O40](3-) complex was stable only at P(V) concentrations <7 mM; further addition of P(V) caused the [PMo12O40](3-) complex to decompose mainly into the A-[PMo9O34H6](3-) complex at an ambient temperature. The latter was subsequently converted into the Dawson-type [P2Mo18O62](6-) complex at an elevated temperature; the Dawson complex was kinetically stable even in the presence of excess of P(V). At As(V) concentrations <10 mM, in contrast, the corresponding Mo(VI)-As(V) system did not produce the Keggin-type [AsMo12O40](3-) complex but the previously unknown complex (tentatively formulated as [AsMo10O37H5](4-)) at an ambient temperature; with further addition of As(V), the [AsMo10O37H5](4-) complex was transformed directly into the [As2Mo6O26H2](4-) complex. The Dawson-type [As2Mo18O62](6-) complex, which was formed upon heating the system at 80 degrees C for 5 h, also underwent subsequent transformation into the [As2Mo6O26H2](4-) complex at As(V) concentrations >20 mM. (C) 1999 Elsevier Science S.A. All rights reserved.

Multicomponent polyanions. 53. Structure of tetrakis(trimethylammonium) tetra-mu-oxo-bis(triaquahexadecaoxo(trioxophenylphosphato)hexamolybdate) dihydrate, [NH(CH3)(3)](4)[{(C6H5P)Mo6O21(H2O)(3)}(2)].2H(2)O

DG Lyxell, D Bostrom, M Hashimoto, L Pettersson

ACTA CRYSTALLOGRAPHICA SECTION B-STRUCTURAL SCIENCE ( MUNKSGAARD INT PUBL LTD )  54   424 - 430   1998.08  [Refereed]

　View Summary

The title compound crystallized in the monoclinic space group P2(1)/n (No. 14) [a = 11.211 (5), b = 12.862 (3), c = 23.05 (1) Angstrom, beta = 94.37 (3)degrees, V = 3314 (2) Angstrom(3), Z = 2]. The polyanion can be regarded as a dimer of a phenylphosphonatohexamolybdate, (C6H5P)Mo6O23(H2O)(3), Linked by four O atoms. In this monomeric unit the six molybdenum octahedra are grouped into two parts consisting of four and two edge-sharing octahedra, respectively. These two parts are connected by two corner-sharing O atoms to form a bent Mo-6 ring. The phenylphosphonate group coordinates to the Mo-6 ring from the narrow side as a tripodal Ligand. The {(C6H5P)Mo6O21 (H2O)(3)}(2) units form layers parallel to (001) and the structure is stabilized by hydrogen bonds between water and neighboring anions. The monomeric unit has been shown to be a key structure in the process of deducing the aqueous solution structures of the (C6H5P)Mo-6(2-) and (C6H5P)Mo-7(4-) species found in a previous equilibrium study of the H+-MoO42-(C6H5P)O-3(2-) system.

Voltammetric determination of vanadium(V) and vanadium(IV) through the formation of a 12-molybdovanadate(V) complex

S Himeno, K Kusuyama, M Hashimoto, N Ishio

ANALYTICAL SCIENCES ( JAPAN SOC ANALYTICAL CHEM )  14 ( 4 ) 681 - 685   1998.08  [Refereed]

　View Summary

A simple voltammetric method has been developed for the determination of V(V) and V(IV). When a mixture of V(V) and V(IV) is added last of all to a 50 mM Mo(VI)-0.3 M HCl-70%(v/v) CH3CN system, only V(V) reacts with Mo(VI) to form a 12-molybdovanadate(V) complex which undergoes a two-step reduction at the glassy carbon (GC) electrode; the reduction current is directly proportional to the V(V) concentration in the mixture. On the other hand, when HCl is added last after heating the Mo(VI)-CH3CN system containing a mixture of V(V) and V(IV) at 60 degrees C for 10 min, V(IV) is completely oxidized to V(V), and the total concentration of vanadium is determined. The V(IV) concentration is determined by subtracting the V(V) concentration before oxidation from the total concentration of vanadium. Interferences from foreign ions are also discussed.

Syntheses, structures and solution dynamics of anionic 5-coordinate Pt(II) complexes with halide

S Okeya, M Hashimoto, T Matsuo, K Yamanaka, T Sumino, H Hashimoto, N Kanehisa, Y Kai

CHEMISTRY LETTERS ( CHEMICAL SOC JAPAN )  ( 6 ) 541 - 542   1998.06  [Refereed]

　View Summary

Five-coordinate anionic complexes, [Pt(hfac)(2)X](-) (X = Cl, Pr, I), were prepared by reaction of [Pt(hfac)(2)] and [PPh4]X in CH2Cl2. A distorted square pyramidal structure was revealed by the X-ray analysis. The variable-temperature H-1 and F-19 NMR spectra of these complexes were explained by two independent dynamic motions in solution, which were considered good models for the ligand exchange and cis-trans isomerization reactions.

Multicomponent polyanions. 54. Crystal structure of tetracaesium monohydrogen phosphato(phosphito)pentamolybdate dihydrate, Cs-4[H(HP)PMo5O22]center dot 2H(2)O

DG Lyxell, D Bostrom, M Hashimoto, L Pettersson

ACTA CHEMICA SCANDINAVICA ( MUNKSGAARD INT PUBL LTD )  52 ( 4 ) 425 - 430   1998.04  [Refereed]

　View Summary

The crystal structure of tetracaesium monohydrogen phosphato (phosphito)pentamolybdate dihydrate was determined by single-crystal X-ray diffraction. The compound crystallises in the triclinic space group P (1) over bar, a=10.284(2), b= 10.791(2) and c=13.047(3) Angstrom, alpha=109.34(2), beta=99.92(2) and gamma=102.85(2)degrees, V=1283.4(5) Angstrom(3) and Z=2. The final R-values are R=0.066, wR=0.039 and S=1.3667. The H(HP)PMo5O224- anion has common features with the Strandberg X2M5-type heteropolyanion. The five MoO6 octahedra form a five-membered ring by one corner-sharing and four edge-sharing connections, and the tripodal phosphate and phosphite ligands protrude from each side of this ring in opposite directions. This is the first example of the structure of the heteropolyoxometalate having both P-III and P-V as heteroatoms.

均一沈殿法による12-タングストリン酸アンモニウム酸性塩触媒の調製とその構造

犬丸 啓, 中島 仁, 橋本 正人, 御園生 誠

日本化学会誌     390 - 397   1998  [Refereed]

Heteropoly compounds .30. Alkane oxidation with mixed addenda heteropoly catalysts containing Ru(III) and Rh(III)

Y Matsumoto, M Asami, M Hashimoto, M Misono

JOURNAL OF MOLECULAR CATALYSIS A-CHEMICAL ( ELSEVIER SCIENCE BV )  114 ( 1-3 ) 161 - 168   1996.12  [Refereed]

　View Summary

Oxidation of alkanes, mainly of cyclohexane, with t-butyl hydroperoxide (TBHP) catalyzed by alkylammonium salts of mixed addenda heteropoly compounds having Keggin-type polyanions were studied in benzene solutions, with regard to the relative catalytic activity, reaction orders and the stability of catalysts. Tetra-n-hexylammonium salts of SiRu(H2O)W11O395- and SiRh(H2O)W11O395- showed higher catalytic activities than the corresponding Fe- and Go-substituted catalysts for the selective oxidation of cyclohexane to cyclohexanol and cyclohexanone. Although the Ru catalyst was possibly a mixture, it consisted mainly of SiRu(H2O)W11O395- and gave reproducible catalytic performance for repeated preparations. The initial rates were approximately proportional to the concentrations of cyclohexane, TBHP and the catalyst. Although the rate decreased with the consumption of TBHP, the initial rate was resumed by the addition of TBHP, indicating the absence of the deterioration of catalytic activity. Similarly alcohols and ketones were selectively formed from n-decane and ethylbenzene.

DOI

Multicomponent polyanions .48. The crystal structure of trihydrogen dodecamolybdophosphate-benzene(1/3)

DG Lyxell, D Bostrom, M Hashimoto, L Pettersson

ACTA CHEMICA SCANDINAVICA ( MUNKSGAARD INT PUBL LTD )  50 ( 11 ) 985 - 990   1996.11  [Refereed]

　View Summary

A novel organic solvated heteropoly compound, H3Mo12PO40. 3(C6H6), crystallised in the monoclinic form, P2(1)/n (No. 14), with a = 12.189(2), b = 13.981(2), c = 12.978(1) Angstrom and beta = 98.59(1)degrees. The refinement of 340 parameters with 3705 reflections [I > 3.0 sigma(I)] gave a final R-value of 0.061 (R(w) = 0.067). The polyanion, having a so-called alpha-Keggin structure, is disordered around an inversion centre. One of three benzene molecules is sandwiched between polyanions, and the other two are accommodated in a cavity surrounded by polyanions. The links between polyanions and benzene rings are mainly due to hydrogen bonds. The phosphate and benzene in the compound were formed by hydrolysis of phenylphosphonate. (C) Acta Chemica Scandinavica 1996.

Preparation and structure of tetramethylammonium hydrogen triperoxotrimolybdodisulfate trihydrate, [N(CH3)4]3[H(SO4) 2-(MoO2(O2))3]·3H 2O

Masato Hashimoto, Hikaru Ichida, Yukiyoshi Sasaki

Journal of Coordination Chemistry ( Taylor and Francis Ltd. )  37 ( 1-4 ) 349 - 359   1996  [Refereed]

　View Summary

A novel peroxopolyoxomolybdate compound, [N(CH3)4]3 [H(SO4)2 (MoO2(O2))3]·3H2O, has been obtained from a strongly acidic aqueous solution of a molybdate-sulfate system as the monoclinic crystal of P21/n, a = 13.497(3), b = 15.231 (4), c = 32.603(2) Å, β= 103.113(9)°, and V = 6577(2) Å3. The final R-value was 0.0986 for 395 parameters using 7162 reflections. Each of the two crystallographically independent polyanions contains three molybdenum atoms with five O2-, one O2 2-, and two sulfate groups, one of which is a tripod ligand apical to the molybdenum plane, and the other is a bipod ligand equatorial to the Mo plane. © 1996 OPA (Overseas Publishers Association) Amsterdam B.V. Published in The Netherlands under license by Gordon and Breach Science Publishers SA.

DOI

SYNTHESIS AND CHARACTERIZATION OF A BIDENTATE CHELATING DIISONITRILE LIGAND WITH 2 THIOETHEREAL SULFURS IN A BRIDGING GROUP AND ITS COPPER(I), RHODIUM(I) AND PALLADIUM(II) COMPLEXES

K SAKATA, K MATSUMOTO, M HASHIMOTO

INORGANICA CHIMICA ACTA ( ELSEVIER SCIENCE SA LAUSANNE )  227 ( 1 ) 113 - 118   1994.12  [Refereed]

　View Summary

The diisonitrile ligand (L) has been synthesized in five reaction steps from t-butylbenzene with an overall yield of 7.3%. The reaction of palladium(II) chloride with L leads to the palladium(II) complex, PdLCl(2), whereas the rhodium(I) complexes, RhL(2)Cl and RhL(2)BF(4), and the copper(I) complex, CuL(2)BF(4), are prepared by ligand exchange reactions. These complexes were investigated by means of mass, infrared, nuclear magnetic resonance (NMR) and electronic spectra, as well as molar conductances. Judging from the molar conductances of the RhL(2)Cl, RhL(2)BF(4), and CuL(2)BF(4), complexes, tetrafluoroborate and chloride anions are ionized in acetonitrile. This is also supported by mass spectral data. The strong band at 2100 cm(-1) is assigned to the N drop C stretching mode. This band shifts to higher frequency upon metal coordination because of the inductive effect produced by the positive charge of the metal ions. This shift increases with increasing charge on the complex. The methy]ene proton signals of the benzy] group and the bridging group in the ligand are shifted slightly downfield on formation of the complexes. Since the magnitude of the shift is approximately proportional to the oxidation number in the metal complexes, the oxidation number could be distinguished by proton NMR studies of the methy]ene groups. These results indicate that the N drop C group in the ligand serves as a sigma-donor and the thioethereal sulfur in the bridging group is not coordinated to the metal atoms. It is surprising that L does not coordinate through the sulfur atoms rather than the isonitriles, because the S-coordinated form would have a stable five-membered-ring structure and the isonitrile coordination gives a fifteen-membered-ring structure.

CD(2,2'-BIPYRIDINE-N,N')NI(CN)4, A HIGHLY BENT CLOSE 2-DIMENSIONAL NETWORK OF [CD-((NC)NI1/4)4]N

M HASHIMOTO, T IWAMOTO

ACTA CRYSTALLOGRAPHICA SECTION C-CRYSTAL STRUCTURE COMMUNICATIONS ( MUNKSGAARD INT PUBL LTD )  50   496 - 498   1994.04  [Refereed]

　View Summary

The crystal structure of poly[(2,2'-bipyridine-N,N')cadmium(II) tetra-mu-cyanonickelate(II)], [Cd(CoH8N2)][Ni(CN)4], has been determined. The tetracyanonickelate(II) ion, Ni(CN)42-, bridges four Cd+ ions to form an infinite two-dimensional folded network stacking along the b axis. The 2,2'-bipyridine ligands chelate to the Cd atoms alternately above and below the folded network. The distortion about the octahedrally coordinated Cd atom is so large, as a result of the unusual coordination behaviour of the Ni(CN)4 in the network formation, that one of the Cd-N-C angles is markedly bent [143.1 (3)-degrees].

ACID STRENGTH OF HETEROPOLYACIDS AND ITS CORRELATION WITH CATALYTIC ACTIVITY

T OKUHARA, CW HU, M HASHIMOTO, M MISONO

BULLETIN OF THE CHEMICAL SOCIETY OF JAPAN ( CHEMICAL SOC JAPAN )  67 ( 4 ) 1186 - 1188   1994.04  [Refereed]

　View Summary

UV spectrophotometry of a Hammett indicator revealed that the acid strength of the Keggin-type heteropolyacids having W as addenda atoms increased as the valency of the central atom increased (Co < B < Si, Ge < P). The catalytic activity for the decomposition of isobutyl propionate in a homogeneous system was correlated well with the acid strength.

[(C5H5N)2H]3[PW12O40]

M HASHIMOTO, M MISONO

ACTA CRYSTALLOGRAPHICA SECTION C-CRYSTAL STRUCTURE COMMUNICATIONS ( MUNKSGAARD INT PUBL LTD )  50   231 - 233   1994.02  [Refereed]

　View Summary

The crystal structure of tris(dipyridinium) dodecatung-stophosphate has been determined. The [PW12O40]3- heteropolyanion, having T(d) symmetry, is disordered by the 3 symmetry. The pyridine molecules are paired around H+ forming (C5H5N)-H+-(NC5H5) cations with their molecular planes almost parallel to the ab plane of the crystal.

DOI

SELECTIVE OXIDATION OF CYCLOPENTENE AND CYCLOHEXENE BY HYDROGEN-PEROXIDE CATALYZED BY HETEROPOLYACIDS

KY LEE, K ITOH, M HASHIMOTO, N MIZUNO, M MISONO

NEW DEVELOPMENTS IN SELECTIVE OXIDATION II ( ELSEVIER SCIENCE PUBL B V )  82   583 - 591   1994  [Refereed]

　View Summary

Oxidation of cycloolefins by hydrogen peroxide catalyzed by various Keggin-type heteropolyacids, H3PMo12-xWxO40, x=0-12, were studied in homogeneous tri-n-butyl phosphate solution, placing stress on the effects of the constituent elements of heteropoly anion. Remarkable synergistic effect of mixed addenda atoms, Mo and W, was observed and high yields of dialdehyde were obtained. A reaction scheme was proposed based on the time course and stoichiometry of reaction, and the reactivity of products.

CRYSTAL-STRUCTURE OF TETRACAESIUMDIHYDROGENDECAVANADATE TRIHYDRATE, CS4H2V10O28-CENTER-DOT-3H2O - A LAYERED CRYSTAL-STRUCTURE OF DECAVANADATE

M HASHIMOTO, M MISONO, M HIBINO, J OI, T KUDO

POLYHEDRON ( PERGAMON-ELSEVIER SCIENCE LTD )  12 ( 22 ) 2745 - 2747   1993.11  [Refereed]

　View Summary

The title compound Cs4H2V10O28.3H2O was obtained from a polyvanadate system containing H2O2. No peroxo group or hydrogen peroxide molecule was found in the structure. The polyanions are ordered parallel to the bc-plane forming a layered structure. The water molecules and the caesium ions make a hydrogen bonding network with decavanadate ions and each other to support the whole crystal structure.

CATALYSIS BY HETEROPOLY COMPOUNDS .22. REACTIONS OF ESTERS AND ESTERIFICATION CATALYZED BY HETEROPOLYACIDS IN A HOMOGENEOUS LIQUID-PHASE EFFECTS OF THE CENTRAL ATOM OF HETEROPOLYANIONS HAVING TUNGSTEN AS THE ADDENDA ATOM

CW HU, M HASHIMOTO, T OKUHARA, M MISONO

JOURNAL OF CATALYSIS ( ACADEMIC PRESS INC JNL-COMP SUBSCRIPTIONS )  143 ( 2 ) 437 - 448   1993.10  [Refereed]

Second Harmonic Generation in Inorganic-Organic Complexes. 1. Control of Bulk Dipolar Alignment of p-Nitroaniline Crystal upon Complexing with Hydrobromic Acid

Takeshi Gotoh, Noritaka Mizuno, Masakazu Iwamoto, Satoshi Hashimoto, Masahiro Kawasaki, Masato Hashimoto, Makoto Misono

Chemistry of Materials   4 ( 3 ) 502 - 504   1992.02  [Refereed]

DOI

THE TWISTED SKELETON OF 1,9-DIAMINONONANE IN CATENA-[CATENA-MU-(1,9-DIAMINONONANE)CADMIUM(II) TETRA-MU-CYANONICKELATE(II)]-O-XYLENE(2/1)A

M HASHIMOTO, T KITAZAWA, T HASEGAWA, T IWAMOTO

JOURNAL OF INCLUSION PHENOMENA AND MOLECULAR RECOGNITION IN CHEMISTRY ( KLUWER ACADEMIC PUBL )  11 ( 2 ) 153 - 158   1991.09  [Refereed]

　View Summary

The Hofmann-danon-type o-xylene clathrate Cd[NH2(CH2)9NH2]Ni(CN)4.0.5(CH3)2C6H4, crystallizes in the triclinic space group P1BAR with a = 15.118(3), b = 14.048(4), c = 7.325(1) angstrom, alpha = 91.50(2), beta = 131.66(3), and gamma = 107.50(2)-degrees, V = 1051(1) angstrom 3 and Z = 2. The structure, refined to R = 0.047 using 2851 reflections, reveals a three-dimensional host framework built of the layers of a two-dimensional catena-[cadmium tetra-mu-cyanonickelate(II)] network and of the ambidentate 1,9-diaminononane (danon) bridging the Cd atoms in adjacent networks. The guest o-xylene molecule is accommodated in the cavity formed in the interlayer space similar to that in the Hofmann-daotn-type. The skeleton of the danon in the Cd-NC9N-Cd linkage takes a (gauche)2(trans)8 conformation twisted at the (gauche)2 part in contrast with the all-trans conformation of 1,8-diaminooctane in the Hofmann-daotn-type clathrate. The twisted (gauche)2 part of the danon skeleton occupies the interlayer space to such an extent that void space available for the guest o-xylene molecule decreases to half that in the Hofmann-daotn-type clathrate Cd[NH2(CH2)8NH2]Ni(CN)4.G.

DOI

Preparation and X-ray crystal structure of [N(CH3)4]4[{H(SO4)W3O7(O2)2}2O]

Masato Hashimoto, Toschitake Iwamoto, Hikaru Ichida, Yukiyoshi Sasaki

Polyhedron   10 ( 6 ) 649 - 651   1991  [Refereed]

　View Summary

The title peroxotungstosulphate as the first example of a polytungstosulphate has been prepared and its structure determined. The salt crystallizes under the conditions: [WO42-] = 0.3-1.0 mol dm-3, [WO42-]/[SO42-] = 1-1/4, [WO42-]/[H2O2] = 1/2-1/4 and pH &lt
1. The SO42- tetrahedron shares its three vertices with two WO5(O2)2 decahedra and one WO6 octahedron to form a diperoxotritungstosulphate moiety
the polyanion is made of the two moieties bridged with three gm-oxo groups. © 1991.

DOI

CRYSTAL-STRUCTURES OF (18-CROWN-6)-(2-HYDROXYETHYLAMMONIUM) TETRACYANONICKELATE(II) AND 10-AMINODECYLAMMONIUM TETRACYANONICKELTATE(II)

M HASHIMOTO, T IWAMOTO

JOURNAL OF COORDINATION CHEMISTRY ( GORDON BREACH SCI PUBL LTD )  23 ( 1-4 ) 269 - 276   1991  [Refereed]

CATENA-MU-(1,9-DIAMINONONANE)CADMIUM(II) ARRAY IN THE CRYSTAL-STRUCTURE OF CATENA-[BIS-CATENA-MU-(1,9-DIAMINONONANE)CADMIUM(II) CIS-DI-MU-CYANO-DICYANONICKELATE(II)]-(2,4-XYLIDINE) (1/2) DIFFERENT FROM THAT IN THE 2,3-ISOMER ANALOG

M HASHIMOTO, T IWAMOTO

CHEMISTRY LETTERS ( CHEMICAL SOC JAPAN )  ( 9 ) 1531 - 1534   1990.09  [Refereed]

DOI

NOVEL 3-DIMENSIONAL METAL-COMPLEX HOST STRUCTURES OF CATENA-[PROPYLENEDIAMINECADMIUM(II) TETRA-MU-CYANONICKELATE(II)] AND CATENA-[PROPYLENEDIAMINECADMIUM(II) TETRA-MU-CYANOCADMATE(II)]

KM PARK, M HASHIMOTO, T KITAZAWA, T IWAMOTO

CHEMISTRY LETTERS ( CHEMICAL SOC JAPAN )  ( 9 ) 1701 - 1704   1990.09  [Refereed]

IR, RAMAN AND C-13 NMR-SPECTRA OF PEROXOTUNGSTOOXALATE

M HASHIMOTO, T IWAMOTO, H ICHIDA, Y SASAKI, T KUDO

INORGANICA CHIMICA ACTA ( ELSEVIER SCIENCE SA LAUSANNE )  166 ( 1 ) 17 - 20   1989.12  [Refereed]

DOI

CRYSTAL-STRUCTURE OF CATENA-[CATENA-BIS-MU-(1,9-DIAMINONONANE)CADMIUM CIS-DI-MU-CYANO-DICYANONICKELATE(II)]-(2,3-XYLIDINE)(1/2)

M HASHIMOTO, T HASEGAWA, H ICHIDA, T IWAMOTO

CHEMISTRY LETTERS ( CHEMICAL SOC JAPAN )  ( 8 ) 1387 - 1390   1989.08  [Refereed]

OXALATO COMPLEXES DIRECTLY FORMED BY THE REACTION OF INTERSTITIAL CARBIDES WITH HYDROGEN-PEROXIDE

T KUDO, Y SASAKI, M HASHIMOTO, K MATSUMOTO

INORGANICA CHIMICA ACTA ( ELSEVIER SCIENCE SA LAUSANNE )  145 ( 2 ) 205 - 209   1988.05  [Refereed]

DOI

FORMATION OF PEROXO OXALATO COMPLEX OF TUNGSTEN(VI) DIRECTLY FROM TUNGSTEN CARBIDE AND HYDROGEN-PEROXIDE - A NEW PATH TO THE TOTAL SYNTHESIS OF THE ORGANIC-COMPOUND

T KUDO, Y SASAKI, M HASHIMOTO, H ICHIDA, K MATSUMOTO

INORGANICA CHIMICA ACTA ( ELSEVIER SCIENCE SA LAUSANNE )  133 ( 2 ) 201 - 203   1987.10  [Refereed]

CRYSTAL-STRUCTURE OF TETRABUTYLAMMONIUM MU-OXALATOBIS(OXODIPEROXOTUNGSTATE) (2-), [(N-C4H9)4N]2[WO(O2)2(C2O4)WO(O2)2]

M HASHIMOTO, T OZEKI, H ICHIDA, Y SASAKI, K MATSUMOTO, T KUDO

CHEMISTRY LETTERS ( CHEMICAL SOC JAPAN )  ( 9 ) 1873 - 1876   1987  [Refereed]