Search

Aim.The efficacy of the short hydration regimen was reported in chemotherapy containing intermediate- to high-dose cisplatin, and the use of outpatient chemotherapy containing cisplatin with short hydration has been widespread in recent years.Methods.We compared patients with gastric cancer, lung cancer, and urothelial cancer who received outpatient chemotherapy containing cisplatin (≥60 mg/m2/cycle) with the short hydration regimen since April 2012(n=13)with those who received hospital chemotherapy with continuous hydration between April 2011 and March 2013(n=17)in our hospital.Results.Grade 2 or higher acute kidney injury occurred in 2 patients in the continuous hydration group and in no patient in the short hydration group; 1 patient discontinued treatment on account of nephrotoxicity. There was no difference between the 2 groups in maximum creatinine increment and maximum clearance decrement. Relative dose intensity in the short hydration group was higher than that in the continuous hydration group (89.5% versus 80.3%;P<0.01).Conclusions.The short hydration regimen in outpatient chemotherapy containing intermediate- to high-dose cisplatin is as safe as the continuous hydration regimen and increased the efficacy of chemotherapy.

A silicon interposer with an integrated with SrTiO3 (STO) thin film capacitor that decreases switching noise in high-speed digital circuits has been developed, along with a process to fabricate it. The process for fabricating the capacitor was optimized to reduce the defect density. The identified optimal process conditions are sputter-depositing the STO at 400 °C and using Ru as a bottom electrode. An large-scale integration chip is stacked on the Si interposers using chip-to-wafer bonding, and through-silicon vias (TSVs) are then formed in the interposer. This stacking enables a 50 μm-thick Si interposer to be inserted between a chip and a printed wiring board (PWB). A maximum capacitance density of 2.5 F/cm2 was achieved for a 60-nm-thick STO capacitor in a 20 × 20 mm2 area with 9000 TSVs (50- diameter; 50- depth). The capacitance of slightly more than 1 F in interposer-chip stack samples with 1600 TSVs remained constant during a thermal testing on PWBs for up to 1000 cycles.

The crystal and the molecular structures of the title complex were determined by means of the single-crystal X-ray diffraction method. The crystal of PtC28H23O5N2Cl4, F. W. 804.40, (black-violet in color) is monoclinic, with the space group of P21⁄a, a=18.293(4), b=9.682(2), c=15.797(3) A, β=96.55(2)°, U=2779.6(9) A3, Z=4, Dm=1.90, Dx=1.92 g cm−3, and μ (Mo Kα)=57.37 cm−1. The platinum atom is in a hexa-coordinated octahedral geometry, where one 2-(2-benzoxazolyl)phenolate (bxp−) ion is chelated with its N and phenolato O atoms. The bxp− ligand as well as the free Hbxp molecule are both approximately planar, and their planes are approximately in parallel: They are arranged alternately and are laid roughly along the a-axis. Although the overlappling areas of the neighboring rings are only 23 and 13% respectively of the whole ring area, the interplane distances are 3.42 and 3.49 A.

Background and aims: The efficacy of the short hydration regimen was reported in chemotherapy containing intermediate- to high-dose cisplatin, and the use of outpatient chemotherapy containing cisplatin with short hydration has been widespread in recent years. We have provided outpatient chemotherapy containing cisplatin with the short hydration regimen since July 2012. The aim of this study was to evaluate the safety and efficacy of the short hydration regimen. Methods: We compared patients with gastric cancer, lung cancer, and urothelial cancer who received outpatient chemotherapy containing cisplatin (≥ 60 mg/m2/cycle) with the short hydration regimen since July 2012 (n = 13) with those who received hospital chemotherapy with continuous hydration between April 2011 and June 2012 (n = 17) in our hospital. To assess the incidence of cisplatin nephrotoxicity and the effect of the treatment, serum creatinine and creatinine clearance levels were monitored and relative dose intensity (RDI) was calculated. Results: There was no difference between the 2 groups with respect to the background factors. Grade 2 or higher acute kidney injury occurred in 2 patients in the continuous hydration group and in no patient in the short hydration group; 1 patient discontinued treatment on account of nephrotoxicity. There was no difference between the 2 groups in the average value of maximum creatinine increment (0.14 mg/dl vs. 0.32 mg/dl; p = 0.43) and maximum clearance decrement (10.9 ml/min vs. 18.3 ml/min; p = 0.28). RDI in the short hydration group was higher than that in the continuous hydration group (89.5% vs. 80.3%; p Conclusions: The short hydration regimen in outpatient chemotherapy containing intermediate- to high-dose cisplatin is as safe as the continuous hydration regimen, and increases the efficacy with the convenience of chemotherapy scheduling.

The titled series of isomorphous complexes, the first octakis(isothiocyanato) complexes of lanthanoids, were obtained. Their crystals are tetragonal, space group P4nc, Z=2. The cell dimensions of the praseodymium complex, for example, are a=15.871(7), c=11.543(6) A, U=2908(3) A3, and Dm=1.29(3), Dx=1.29 g cm−3, μ(MoKα)=11.60 cm−1, with a final R value of 0.069. The metal atom is octa-coordinated by eight isothiocyanate ions in an intermediate geometry between cube and square-antiprism. The benzene included in the praseodymium complex crystals was retained up to 174°C (DTA), and was not removed even after being heated for 12 h at 110°C. In cases of the other isomorphous members, the benzene was removed at lower temperatures, respectively. The isomorphous fluorobenzene adduct was obtained only for the lanthanum complex.

The crystal and molecular structures of the chloroacetato complexes of gadolinium(III), erbium(III), and ytterbium(III) indicated in the title were determined by the single-crystal X-ray diffractio...

The new complexes indicated in the title have been synthesized, and the crystal and molecular structure of the neodymium(III) complex has been determined by the X-ray diffraction method. The crystal is monoclinic, with the space group C2/c, Z=16, a=28.887(4), b=28.913(5), c=24.814(5)A, β=106.72(1)°. The final R value for 7761 reflections is 0.066. The central neodymium(III) atom of the complex is octa-coordinated and is in a dodecahedron geometry; three O,O′-diisopropyl dithiophosphato ligands, chelating by both of the sulfur atoms, span the two m edges of a trapezium as well as one a edge of the other trapezium, and two oxygen atoms of both the benzamide ligate at both tips of the base edge of the latter trapezium. The solid and the acetonitrile solution of the europium(III) complex are orange in color, and they show a charge-transfer band in their near-ultraviolet absorption spectra.

The structure of the title complex was determined by the single-crystal X-ray-diffraction method. It is triclinic, with the space group P\bar1; the cell constants were a=12.529(2), b=15.044(4), c=10.063(1) A, α=104.15(2), β=98.73(1), and γ=87.16(2)°; Z=1, and the final R value was 0.053. The central metal atom is in a tricapped trigonal-prism geometry and is ennea-coordinated with seven oxygen atoms of the carboxylate ligands and with each oxygen atom of one water and one ethanol molecule. The complex is dimeric and the metal atoms are bridged with four carboxylate ions; two of them act as bidentates, and the other two, as tridentates, where one oxygen atom is coordinated to both metal atoms. The other carboxylate ion makes a chelate ring with each metal atom. The dimer is connected through hydrogen bondings to the atoms on both sides along the c-axis.

The title complex, obtained as the first characterized solid Os(IV)-edta complex, crystallizes in the monoclinic space group P21/a with a=14.956(7), b=8.181(3), c=14.600(7) A, β=126.64(3)°, and Z=4. In the complex molecule [Os(edta)(H2O)], the seven-coordinate Os(IV) sits in a monocapped trigonal prism formed with two N and four O atoms of sexidentate edta and with an O atom of H2O.

The crystal and molecular structure of the title complex was determined by a single-crystal X-ray diffraction technique. The crystal is triclinic with a space group P\bar1, a=11.323(4), b=18.383(10), c=9.284(5) A, α=104.62(4), β=114.26(3), γ=77.71(4)°, Z=4; the final R value obtained was 0.034. All cadmium atoms are lined approximately along the [111] axis and each pair of metal atoms are bridged by two thiocyanate ions (SCN), one of which is S-coordinated and the other is N-coordinated to the same side metal atom. Also bonded with two nitrogen atoms of 4-methylpyridine (pic) ligands, the metal atom is 4N2S-hexa-coordinated and is in an octahedral geometry. The cadmium atoms, where the ligated respective pairs of N(SCN), N(pic), and S(SCN) atoms are all in a trans configuration, and the metal atoms where the ligated respective pairs of N(pic) and S(SCN) are in cis, while the pair of the N(SCN) in trans configuration, appear alternatively in the polymer chain.

N-Methyl-2-piperidone adduct and dimethyl sulfoxide adduct of cobalt(II)mercury(II) thiocyanate were synthesized and their crystal and molecular structures were determined by the single-crystal X-ray diffraction technique. The former adduct is triclinic with a space group P\bar1, a=8.488(3), b=17.206(7), c=8.466(3) A, α=103.72(1)°, β=90.00(1)°, γ=100.85(1)°, Z=2, while the latter adduct is orthorhombic with a space group P212121, a=8.418(3), b=27.389(10), c=8.407(3) A, Z=4, and the final R values obtained were 0.059 and 0.066, respectively. In these adducts each mercury atom is in the tetrahedral geometry, coordinated with four sulfur atoms of the thiocyanate (SCN) ions, and each cobalt atom is in the octahedral geometry, coordinated with four nitrogen atoms of SCN ions and two oxygen atoms of the Lewis-base molecules which occupy the trans-positions. Each pair of different kinds of metal atoms are bridged by an SCN ion forming a 16-membered ring of Co2Hg2(SCN)4; these are linked, forming a two-dimensiona...

Five isomorphous lanthanoid(III) complexes were synthesized, and the structure of the terbium (1) and erbium (2) complexes were determined by the use of the single-crystal X-ray diffraction method. Crystals of 1 and 2 are monoclinic, with the space group P21/n, and the cell constants are: (1) a=25.076(8), b=15.446(3), c=14.579(8) A, β=100.77(4)°; (2) a=25.036(20), b=15.228(4), c=14.805(19) A, β=99.50(12)°. The structures were solved by the heavy-atom method and refined by the block-diagonal least-squares method. The final R values of 1 and 2 are 0.061 and 0.055 respectively. They consist of discrete complex cations and dithiophosphate anions. The central metal atom of the cationic complex is hepta-coordinated, and it is in a pentagonal bipyramidal geometry, where four sulfur atoms of two dithiophosphate ions and one oxygen atom of a benzamide ligand take the equatorial positions, while two benzamide oxygen atoms are in the axial positions.

The title complexes have been synthesized, and their crystal and molecular structures were determined by the X-ray diffraction method using their single crystals. Among them, the crystals of the La, Ce, and Pr complexes are isomorphous; cubic, space group Pm\bar3, Z=1, and the cell constants of the Pr complex, for example, are a=11.513(2) A, U=1526.1(5) A3, and the final R value was 0.093. The Nd, Dy, and Er complexes, another group of the isomorphous complexes obtained almost by the same synthetic method, are tetragonal, space group I4/m, Z=2, and the cell constants of the Er complex, for example, are a=1.564(2), c=22.627(4) A, U=3026(3) A3, and the final R value was 0.071. The coordination geometry around the metal atoms of both types of complexes are almost the same: seven thiocyanato nitrogen and one water oxygen atoms are coordinated in a cubic geometry, being disordered as if each ligating atomic position is equally occupied by 1/8 atom of the water oxygen and 7/8 atoms of the thiocyanato nitrogen. ...

The title new complexes were synthesized and their crystal and molecular structures were determined by the single-crystal X-ray diffraction method. The crystal form of [(C2H5)4N]3[Yb(NCS)6]·(C6H6), for example, is monoclinic, space group P21⁄c, a=19.458(12), b=14.046(6), c=18.288(7) A, β=91.28(4)°, Z=4, and the final R value obtained was 0.064. The other seven crystals are isomorphous with each other. The central metal atom is in an octahedral hexa-coordination geometry: six nitrogen atoms of isothiocyanate ions are ligated to each metal atom. Each solvent molecule is arranged betweeen each pair of neighboring metal atoms along the [1 \bar1 0] axis in each crystal. The cations are arranged approximately between each pair of metal atoms along the [0 1 1], [0 \bar1 1], and [1 1 0] axes, respectively. They were stable for more than a few weeks at room temperature; however, when heated at about 80–90 °C, their guest molecules were lost.

The crystal and molecular structures of the title complexes were determined by the single-crystal X-ray diffraction method. Both of them are triclinic, with the space group P\bar1. The crystallographic data: 2-methylpyridine (α-pic) adduct, a=11.076(3), b=18.478(8), c=9.299(3)A, α=104.60(3), β=114.84(2), γ=81.12(3)°, Z=4, final R value is 0.037; 3-methylpyridine (β-pic) adduct, a=8.7667(16), b=16.655(4), c=5.8447(10)A, α=91.406(18), β=100.571(14), γ=92.525(18)°, Z=2, final R value is 0.041. In both complexes, all cadmium atoms are in 4N2S-hexa-coordination, being in an octahedral geometry; they are oriented as any pair of side-by-side metal atoms being bridged by two thiocyanate ions. In the α-pic adduct, the chain is oriented approximately along the [111] axis. In the chain, the metal atoms in two kinds of orientations appear alternately: Around one kind of the metal atoms three kinds of ligating atoms are all in trans-configurations, and around the other kind of the metal atoms the respective pairs of N...

The title complex was newly synthesized and its crystal and molecular structure was determined by the single-crystal X-ray diffraction technique. The crystal is monoclinic, space group C2⁄c, a=16.005(4), b=10.520(2), c=15.338(4) A, β=114.68(2)°, and Z=4. In the complex, the central metal atom is hexa-coordinated being in a deformed octahedral geometry: Two 2-(2-benzoxazolyl)phenolato ligands form six-membered chelate rings being coordinated with their oxazolyl nitrogen and phenolato oxygen atoms, while the nitrate ion acts as a bidentate with its two oxygen atoms. As the benzoxazolyl ring is parallel and overlapped with that of the neighboring complex along the c-axis, where the interplane distance is 3.557 A, some interaction between the rings is expected. As this complex in solid state is deep violet, almost black, in color, some charge-transfer bands are expected to exist in its electronic spectra. The bis[2-(2-benzothiazolyl)phenolato]nitratoiron(III) was found to be isomorphous to the title complex.

The crystals of the title complex resolve spontaneously. The enantiomeric crystals were separated under a microscope. They are orthorhombic, space group P212121. This is a square planar complex with 2Cl in cis-positions. The ligand acts as a unidentate with its N atom. The absolute configuration was correlated with the CD spectrum in microcrystalline state.

The title complexes were synthesized and their crystal and molecular structures were determined by the X-ray diffraction method using their single crystals. The crystals of the former ten hexakis(isothiocyanato) complexes of lanthanum through dysprosium(III) and erbiun(III) are isomorphous with each other: monoclinic, space group P21, Z=2. The central metal atom is octa-coordinated, in a square-antiprism geometry, to six nitrogen atoms of thiocyanato (SCN) ions and two oxygen atoms of methanol and water molecules. The two oxygen atoms take the positions of the most approaching apexes of two squares. The latter three heptakis(isothiocyanato) complexes of dysprosium, erbium, and ytterbium are in another isomorphous form with each other: orthorhombic, space group P21nb, Z=4. The central metal atom is hepta-coordinated, in a deformed pentagonal-bipyramidal geometry, to seven nitrogen atoms of SCN ions.

The title complex was synthesized, and the structure was determined by means of the X-ray diffraction technique. The crystal is triclinic; space group P\bar1, a=9.944(1), b=14.336(2), c=9.759(1) A, α=107.00(1), β=117.35(1), γ=76.55(1)°, Z=2, Dx=1.40, Dm=1.36(3) g cm−3, μ(Mo Kα)=1.08 mm−1. The O-methyl dithiocarbonato ion acts as a unidentate ligand, and it is coordinated with the metal through one sulfur atom. The coordination number of the metal is 3 if the cyclopentadienyl is regarded as a unidentate ligand. A series of [(η-cyclopentadienyl)(O-alkyl dithiocarbonato)(trialkyl- or triarylphosphine)nickel(II)], [Ni(C5H5)(S2COR)(PR′3)], where R=CH3, C2H5, CH3(CH2)2, (CH3)2CH, or CH3(CH2)3; R′=C6H5, C6H5CH2, or CH3(CH2)3, were also obtained. The dissociation of the phosphine ligand of the complexes in solution was studied spectrophotometrically, and it was found that the more electron-donative the alkyl group of the O-alkyl dithiocarbonato ligand is, the weaker the phosphorus-nickel bond is.

The M–O bond lengths and some bond angles of the acetato ligands in the title compounds were compared with each other using their structural data as obtained by the single-crystal X-ray diffraction method. With the increase in the atomic number of the central metal atom, the length of the weakest M–O bond in the bridge increases, even though all the other M–O bonds are shortened. This fact can be explained as follows: as the number of ligating oxygen atoms around the central metal atom is almost at a maximum in these complexes, the sharing space of the tenth coordinating atom on the coordination sphere decreases when the radius of the central metal atom is shortened as a result of the lanthanoid contraction effect.

The title complex was synthesized and its crystal and molecular structure were determined by the single-crystal X-ray diffraction technique. The crystal is orthorhombic with a space group P21nb, a=14.953(4), b=15.955(4), c=7.6838(9) A. The crystal was solvent by means of the heavy-atom method and the final R value was 0.059. The mercury atom is in the tetrahedral geometry, coordinated with four sulfur atoms of the thiocyanate (SCN) ions, and the cobalt atoms is in the octahedral geometry, coordinated with four nitrogen atoms of SCN ion and two oxygen atoms of N-methylformamide which occupy the cis positions. Each pair of different kinds of metal atoms is bridged by an SCN ion and are in a three-dimensional network. Twenty-four membered rings of Co3Hg3(SCN)6, where the metal atoms are arranged hexagonally in a chair-form, are condensed two-dimensionally approximately parallel to the (100) plane. All mercury atoms on one plane are bridged by SCN ions to the cobalt atoms of the polymeric plane next to the [1...

The crystal and molecular structure of tetrakis{(isopropylthio)acetato}bis(quinoline)dicopper(II) (1), bis(dibenzylamine)bis{(ethylthio)acetato}copper(II) (2), and bis{(isopropylthio)acetato}tris(isoquinoline)copper(II) (3) were determined by the X-ray diffraction method. The final R values obtained are 0.041, 0.055, and 0.078 for 1, 2, and 3 respectively. 1 is green in color and is orthorhombic with the space group Pcab. It has a dimer structure similar to that of the copper(II) acetate hydrate, where four (alkylthio)acetate liagnds bridge both copper(II) atoms. 2 is violet in color and is monoclinic with the space group A2/a. It has a square-palnar geometry, and no atoms are coordinated to the copper(II) atom from the axial direction, probably because of the steric effect of the large dibenzylamine molecules. 3 is blue in color and is triclinic with the space group P\bar1. It has potentially a hepta-coordinate geometry, where one nitrogen atom and two oxygen atoms ligate from the axial direction of the ...

Several amine or phosphine adducts of bis (O,O′-dialkyl dithiophosphato)cobalt(II), which were hardly oxidized in air at room temperature, were obtained as crystalline solids. The crystal and molecular structure of one adduct, Co(Me2dtp)2(triphenylphosphine) (Me2dtp=O,O′-dimethyl dithiophosphato group), was determined by means of the X-ray diffraction method. The crystal is monoclinic: space group P21/n, a=26.712(4), b=9.495(1), c=11.180(5) A, β=95.43(3)°, Z=4, Dx=1.495, Dm=1.45 g cm−3, μ(Mo Kα)=1.17 mm−1, and the final R value obtained is 0.062 for 4466 observed reflections. The coordinated atoms around the cobalt atom are in a trigonal bipyramidal configuration. The approximate first formation constants of the adducts, K=[Co(II)(R2dtp)2·X]/{[Co(II)(R2dtp)2][X]} (R=alkyl group, and X=donor) in solution, were obtained by means of the spectrophotometric as well as the NMR technique.

Two types of lanthanoid(III) m-hydroxybenzoates, indicated in the title, have been synthesized, and the crystal and molecular structures of four representative complexes, where M=La (1), Nd (2), Sm (3), and Er (4), were determined by the single-crystal X-ray diffraction method. They are all triclinic, space group P\bar1, and the cell constants are as follows: (1) a=12.351(11), b=15.533(10), c=9.250(4) A, α=109.86(4), β=101.40(6), γ=62.95(6)°; (2) a=12.287(4), b=15.542(7), c=9.194(3) A, α=109.64(3), β=101.46(3), γ=62.83(3)°; (3) a=10.580(1), b=12.006(5), c=10.105(2) A, α=111.14(2), β=90.27(1), γ=97.16(2)°; (4) a=10.586(4), b=11.943(6), c=10.027(5) A, α=111.11(3), β=90.53(4), γ=97.26(4)°. The final R values obtained were (1) 0.039, (2) 0.038, (3) 0.030, and (4) 0.039. The central metal atoms of both types of complexes are octa-coordinated, and each is in a square-antiprism geometry. In 1 and 2, one free acid molecule is present, and the molecule is hydrogen-bonded to the oxygen atoms of the coordinated wate...

The crystal and molecular structure of the title complex has been determined by the X-ray diffraction method. The crystal was triclinic, space group P\bar1, a=12.80(1), b=16.65(1), c=8.659(9) A, α=...

The crystal and molecular structure of the two new thiocyanatocadmate(II) complexes indicated in the title were determined by the single-crystal X-ray-diffraction technique. [(CH3)4N]2[Cd(SCN)4] is tri-clinic, with a space group of P\bar1; a=7.300(2), b=13.019(4), c=5.8920(9) A, α=96.32(2), β=93.080(18), γ=104.63(2)°, and Z=1, while [(CH3)4N][Cd(SCN)3] is orthorhombic with a space group of Pna21; a=10.506(3), b=13.797(5), c=9.4506(18) A, Z=4. In both complexes, the cadmium atom is in an octahedral geometry. In 1, the metal atom is at the center of symmetry, and respective pairs of side-by-side metal atoms are bridged by two thiocyanate (SCN) ions, where one SCN ion is S-coordinated and the other is N-coordinated to the same-side metal atom. Also bonded with two nitrogen atoms of unidentate SCN ions, the metal atom is 4N2S-hexa-coordinated, and they line up along the c-axis in a polymeric form. In 2, respective pairs of side-by-side metal atoms are bridged by three SCN ions, two of those SCN ions being S-c...

The title complexes have been synthesized and their crystal and molecular structures determined by a single crystal X-ray diffraction technique. [(C2H5)4N][Cd(SCN)3] (1) is orthorhombic with a space group of A21am; a=10.773(2), b=16.574(4), c=9.871(2) A, and Z=4, while [(C3H7)4N][Cd(SCN)3] (2) is triclinic with a space group of P\bar1; a=10.297(5), b=11.542(5), c=9.374(3) A, α=90.10(3), β=91.61(4), γ=80.94(4)°, and Z=2. In 1, the metal atom has a 3N,3S-hexa-coordinated octahedral geometry, and three ligated N atoms take fac-configuration. Each pair of a metal atoms are bridged by three thiocyanate (SCN) ions, where two SCN ions are S-coordinated, while the other is N-coordinated to the same side metal atom, forming a linear polymeric form. In 2, the metal atom is in a 3N,2S-penta-coordinated trigonal-bipyramidal geometry, where one non-bridging SCN ion is N-coordinated equatorially, while four bridging SCN ions are ligated with two N (axially), and two S atoms (equatorially), respectively. Each pair of me...

The crystal and molecular structure of the title metal complex was determined by the X-ray diffraction method. The crystal is triclinic, with the space group P\bar1, Z=1, a=11.934(2), b=14.642(9), c=11.801(6)A, α=90.41(5), β=94.04(2), and γ=83.82(2)°. The final R value for 6928 reflections is 0.065. The cobalt(II) ato is in a tetrahedral geometry, ligated by four nitrogen atoms of the thiocyanato (SCN) ligands, while the mercury(II) atom is in a trigonal-bipyramidal geometry, where two phosphorus atoms of both the triphenylphosphine ligands bond axially and three sulfur atoms of SCN’s equatorially; however, these Hg–S bonds are very long. Thus, the pairs of cobalt(II) and mercury(II) atoms are linked by one SCN bridge, forming a sixteen-membered ring of Co2Hg2(SCN)4, and this ring is linked with the next ones on both sides in the a-axis direction with two longer bondings.

Two types of the mixed complexes indicated in the title have been synthesized, and their crystal and molecular structures of the lanthanum (1) and the europium (2) complexes have been determined by the X-ray diffraction method. Both 1 and 2 are monoclinic, space group P21⁄n, and Z=4. 1, a=17.354(7), b=23.336(4), c=10.955(2) A, β=96.04(2)°, final R value calculated from 4870 reflections is 0.069; 2, a=29.846(7), b=20.070(3), c=14.057(3) A, β=92.13(2)°, final R value calculated from 7811 reflections is 0.077. In 1, the central metal atom is octa-coordinated, and is in a dodecahedral geometry, where all O,O′-diisopropyl dithiophosphato ligands (iPr2dtp) span m-edges of the dodecahedron, chelating through both of the respective sulfur atoms. Dimethyl sulfoxide (dmso) ligands occupy the apexes of the other m-edge. In 2, the europium(III) metal atom of the cationic species is hepta-coordinated and is in a pentagonal-bipyramidal geometry where two oxygen atoms of dmso ligate from respective ends of the axis and ...

The crystal and molecular structure of the title complex has been determined by X-ray diffraction using 1882 reflections. The crystal was orthorhombic, with the space group Pbn21; a=10.98(2), b=18.496(4), c=7.341(9), Z=4, Dx=1.99, Dm=1.98(2) g cm−3,μ(Mo Kα)=19.3 cm−1, and the final R value was 0.036. A distorted ψ-pentagonal bipyramid is formed around the central antimony(III) atom by two nitrogen and two oxygen atoms, together with a lone electron pair at the equatorial positions and two oxygen atoms at the axial positions. One of the Sb–O distances, 2.78 A, is longer than the others (2.20(2) A on the average), and it is determined that the carbonyl oxygen is essentially of the free-acid type and that its carbonyl oxygen is weakly coordinated. The splitting of the νas(COO) band of its infrared and Raman spectra shows the existence of both free and coordinated carboxyl groups. The 1H- and 13C-NMR results show that the antimony(III)–edta complex does not exchange with the free ligand in an aqueous solution...

The title complex was synthesized, and its crystal and molecular structures were determined by the single-crystal X-ray-diffraction method. It is triclinic, with the space group of P\bar1; the cell constants are a=20.621(4), b=22.288(5), c=7.724(1) A, α=93.30(2), β=96.78(2), γ=107.43(2)°, Z=4, and the final R value is 0.048. Although there are two kinds of crystallographically independent complexes, their structures are almost the same, with only a slight difference in the orientations of the naphthalene rings of the ligands. Both of the central metal atoms are ennea-coordinated and are in the tricapped trigonal-prism geometry: two carboxylato ligands make four-membered chelate rings, and they are also ligated five water oxygen atoms. No carboxylate ions bridge the metal atoms, but the oxygen atoms of the ligands, isolated carboxylate ions, and the crystalline water molecules are linked through hydrogen bondings along the bc-plane. The metal atoms lie on a plane parallel to (100), and the planes are separ...

The title complex was synthesized, and the crystal structure was determined by means of the X-ray diffraction technique. The crystal is monoclinic; space group P21/n, a=16.310(3), b=6.777(1), c=14.576(3) A, β=96.13(1)°, Z=2, Dx=1.58, Dm=1.55(3) g cm−3, μ(Mo Kα)=1.12 mm−1. The molecule has a center of symmetry, and a distorted octahedron is formed around the central cadmium atom; two O,O′-diethyl dithiophosphato ions (dtp) act as bidentate ligands, and each ligand forms a four-membered chelate ring with its two sulfur atoms on the equatorial plane, while two hexamethylenetetramine molecules are coordinated to the metal atom by their nitrogen atoms from the axial direction. Related adducts, Cd(II)(dtp)2·Xn, where X is a donor and n=1 or 2, were also synthesized, and their structures were compared with those of the corresponding Co(II)(dtp)2·Xn−type complexes.

The new complex indicated in the title has been synthesized, and its crystal and molecular structure has been determined by the X-ray diffraction method. The crystal was triclinic; space group P\bar1, Z=2, a=23.071(9), b=11.060(11), c=10.793(13) A, α=120.0(1), β=97.2(2), γ=88.9(2)°. The final R value for 5969 reflections is 0.047. The central lanthanum(III) atom is an octa-coordination and in a dodecahedron geometry, being coordinated with six sulfur atoms of three O,O′-diisopropyl dithiophosphate ligands (iPr2dtp), which span at three m edges, and with two oxygen atoms of both the N,N-dimethylacetamide ligands (dma) at both ends of the remaining m edge. The other [Ln(iPr2dtp)3L2]-type complexes, where Ln=La or Nd; L=dma or N,N-dimethylformamide, have also been obtained. The P=S double bond of the iPr2dtp ligand in the title complex is almost completely delocalized.

Scandium(III) p-toluenesulfonate hexahydrate, as well as the isomorphous yttrium(III) and six lanthanoid(III) (Sm, Gd, Dy, Ho, Er, and Yb) p-toluenesulfonate enneahydrates, were synthesized and the...

The crystal and molecular structures of the chloroacetato–dimethyl sulfoxide (dmso) mixed complex of neodymium(III) indicated in the title were determined by the single-crystal X-ray diffraction method. The crystal is monoclinic, space group P21⁄n, a=21.106(21), b=15.871(8), c=15.748(7) A, β=93.29(5)°, Z=4 (including 12 metal atoms in a unit cell). There are three kinds of crystallographically independent metal atoms, Nd(1), Nd(2), and Nd(3): Nd(1) and Nd(3) are ennea-coordinated (approximately tricapped trigonalprism geometry), and Nd(2) is deca-coordinated (approximately bicapped square-antiprism geometry) including a slightly long M–O bonding. All dmso molecules are directly coordinated to the metal atoms as unidentate, while all the carboxylate ions bridge metal atoms acting as bidentate or tridentate ligands. The bridging atoms are arranged in a chain which is approximately formed along the [101] axis. Also, the isomorphous lanthanum(III) and praseodymium(III) complexes were obtained and their struct...

The crystal and molecular structure of the title complex has been determined by the X-ray diffraction method. The crystal was triclinic, space group P\bar1, a=6.750(2), b=9.214(4), c=5.206(2) A, α=102.57(6), β=103.44(6), γ=100.70(3)°, Z=1, DX=1.702(3), Dm=1.72(3) mg m−3, μ(Mo Kα)=1.89 mm−1, and the final R value was 0.034 for 1175 reflections. The molecular arrangement has a center of symmetry and a distorted octahedron is formed around the central cobalt(II) atom; each methylthioacetato ligand forms a chelate ring by coordinating through a sulfur atom and a carbonyl oxygen atom, and two water molecules also coordinate to the central metal. Its amorphous anhydride as well as the other type anhydride, which resembles the bis(propylthioacetato)cobalt(II) hexamer in its infrared and visible spectra, is obtained by the dehydration process.

An EDTA back-titration of rhodium(III) has been proposed taking advantage of rapid chelation in water-ethanol solutions. The optimum amount of rhodium was 0.5 – 10 mg and the standard deviation was 0.76%. The method is applicable to the analysis of some rhodium(III) complexes.

The 1:1 triphenylphosphine, hexamine, piperazine, pyrazine, and benzothiazole adducts, as well as the 2:1 benzothiazole and benzimidazole adducts of bis(O,O′-diethyl dithiophosphato)cobalt(II) were obtained as crystalline solids, which were hardly oxidized in air, but partially dissociated in their solutions.

Eight isomorphous 2-naphthalenesulfonato complexes of lanthanoids(III) (Pr, Nd, Sm, Eu, Gd, Dy, Er, and Yb) were synthesized, and the structures of five of them were determined by the single-crystal X-ray-diffraction method. They are monoclinic, with the space group of P21; the cell constants of the PrIII complex, for example, were a=18.228(8), b=7.498(4), c=14.177(9) A, β=107.75(4)°, Z=2, and its final R value was 0.043. The unit-cell size of the complex decreases with the increase in the atomic number of the metal atom. The central metal atom is in a square-antiprism geometry and is octa-coordinated with two unidentate 2-naphthalenesulfonato ligands and six water–oxygen atoms. Nonligated oxygen atoms of the sulfonato ions form hydrogen-bonds with the coordinated and lattice water molecules to form a double-layered network along the ab-plane. All the naphthalene rings stand together to form hydrophobic sheets between the hydrogen-bonding networks.

The new complex indicated in the title was synthesized and its crystal and molecular structures were determined by the use of a single-crystal X-ray diffraction method. The crystal is tetragonal, with the space group P\bar4, and the cell constants are a=12.124(5) and c=7.985(2) A. The structure was solved using the heavy-atom method, and the final R value was 0.039. Two kinds of crystallographically independent mercury atoms in the unit cell are tetra-coordinated and they are in the tetrahedral geometry, where four sulfur atoms of the thiocyanate ions are ligated, respectively. The cobalt atom is hexa-coordinated, and is in an octahedral geometry, where four nitrogen atoms of the thiocyanate ions are coordinated equatorially, and two water oxygen atoms axially. Thiocyanate ions span mercury and cobalt atoms to form two-dimensional networks parallel to the (001) plane. The planar polymeric complexes are linked to the c-axis direction, through hydrogen bonds between coordinated water molecules and N,N-dimet...

The crystal and molecular structures of the hydrated lanthanum(III), neodymium(III), and europium(III) chloroacetates indicated in the title were determined by the single-crystal X-ray diffraction method; these three salts as well as the praseodymium(III) salt are apparently isomorphous. By the same synthetic technique, gadolinium(III) or heavier lanthanoid(III) did not give the isomorphous salts. Their crystals are monoclinic with the space group of P21⁄c, and the cell constants of the neodymium(III) salt, for example, are, a=14.805(4), b=18.765(4), c=14.403(5) A, β=95.13(3)°. There are crystallographically independent three kinds of nine-coordinated metal atoms: Nd(1), Nd(2), and Nd(3). Among them, Nd(1) and Nd(2) are best approximated as being in a tricapped trigonal prism geometry. The Nd(3) is best regarded as being in a monocapped square-antiprism geometry, although one more additional oxygen atom, O(35), approaches one side face. In the lanthanum(III) complex, O(35) is thought to be ligated to La(3...

Two compounds of boron with ethylenediaminetetraacetic acid, H6EDTA(BF4)2 and H4EDTA-(BF3)2, as well as complexes with cyclohexanediaminetetraacetic acid and nitrilotriacetic acid, have been synthesized. Their properties, including their infrared and ultraviolet spectroscopic data, have been investigated and discussed.

New compounds of the type M(C5H7S2)2Cl4, where M is Mn(II) or Hg(II), were obtained by passing hydrogen chloride and hydrogen sulfide through ethanol solutions containing acetylacetone and metal chlorides. Such adducts seem to be isostructural to iron compounds, and are stable in the solid state. They seem to decompose when brought into contact with such solvents as water, methanol and dimethylformamide. Their magnetic susceptibilities show that these compounds are all bivalent. The infrared spectra and electronic spectra resemble those of the dithioacetylacetonato iron compound.

The bromo-3-methyl-5-phenyl-1,2-dithiol-1-ium complexes were obtained from metal benzoylacetonate, using hydrogen sulfide and bromine with a catalyst of hydrogen bromide. These complexes resemble bromo-bis(3,5-dimethyl-1,2-dithiol-1-ium) complexes and many of them are of the high-spin type. The Zn(II) and Cd(II) complexes are of the ML2Br4 type (where M=metal and L=3-methyl-5-phenyl-1,2-dithiol-1-ium), like 3,5-dimethyl-1,2-dithiol-1-ium complexes, while Cu(I) is of the MLBr2 type. However the analytical results shows that the Mn(II), Fe(II) and Co(II) complexes are of the ML2Br3 type. Infrared spectra as well as electronic spectra are shown and discussed.

Some compounds of type M(Lss)2Br4, where M is Mn(II), Fe(II), Co(II), Cu(II), Zn(II) and Cd(II) and HLss are dithioacetylacetone, were obtained by passing hydrogen bromide, adding bromine and passing hydrogen sulfide through an ethanolic solution containing an anhydrous metal bromide and acetylacetone. Such compounds, which seem to be isostructural with tetrachlorobis-(dithioacetylacetonato)iron(II), are stable. They are all of high spin, and their infrared spectra show characteristic bands at about 1200, 1000 and 860 cm−1. CuI(Lss)2Br3 was also obtained from cupric bromide by the same method without using bromine, but from cupric chloride, an isostructural complex was not obtained but [Cu(C5H8S2)Cl]n. Electronic spectra are also shown and discussed.

Derivatives of acetylacetonato-nickel(II) in which the coordinating oxygen is replaced by sulfur to various extents have been isolated by the reaction between nickel(II) acetylacetonate and hydrogen sulfide in an ethanolic solution, using hydrogen chloride as the catalyst. These compounds are soluble in organic solvents, such as benzene, acetone, or carbon tetrachloride, but can hardly be dissolved in water. The proton magnetic resonance spectra indicate that the proton of the methyl group attached to the C=S carbon gives greater chemical shifts than that of the methyl group attached to the C=O carbon. The infrared spectra of these compounds are discussed with particular reference to the C=S stretching bands. The electronic spectra of these compounds and the Huckel LCAO-MO calculation of bis dithio compounds are also compared.

The ionic state of polonium(IV) in hydrochloric and sulfuric acid solution was studied by the solvent extraction with hexone (methyl isobutyl ketone).1) The polonium solution stored in 0.4 N nitric acid is strongly hydrolysed by aging. The low extraction coefficient caused by hydrolysis became higher by heating the polonium solution in stronger nitric acid. On the other hand, the polonium stored in 6 N nitric acid can be extracted with constant extraction coefficient, about 80%, through the entire acidity range from 1 to 6 N., if the extraction was carried out without any aging.2) The aging effect of polonium(IV) in hydrochloric acid is rather complicated. A minimum extraction appeared in the acidity range near 2 N hydrochloric acid. By applying mass action law the probable form of polonium(IV) in that range was Po(OH)2Cl42− or PoO2+, assuming that PoCl62− was the stable form of polonium(IV) in 6 N hydrochloric acid which is readily soluble in hexone.3) Almost no polonium(IV) was extracted by hexone from ...

Some new metal chelate compounds of ethanediylidenetetrathiotetraacetic acid (H4ETTA), Co2L·5H2O, Cu2L·4H2O, Zn2L·3H2O, Ni2L·6H2O, and FeHL·3.5H2O, where H4L is H4ETTA, were obtained. The infrared spectra and other properties of these compounds were compared with those of the metal complexes of other thioglycolic acid derivatives, some of which are also new compounds. Judging from the wave numbers of the stretching bands, the carboxyl group of these complexes can be said to be rather ionic. Though the bond is not very strong, thioglycolic acid derivatives seem to bond with the central metal ion with both the sulfur atom and the carboxyl group.

Copper(II), nickel(II), and cobalt(II) complexes of alkylthioglycolic acids, R·S·CH2COOH (where R=ethyl, n-propyl, isopropyl, n-butyl, isobutyl, and s-butyl), were synthesized. Except for some copper complexes, these are new compounds. The attempt to synthesize the solid zinc complexes by the same method has not yet been successful. The relative stabilities of these complexes in the solid state seem to be Zn(II)