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| 1.
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辻井, 宏之 ; 酒寄, 淳史 ; 川幡, 佳一 ; 井原, 良訓 ; Tsujii , Hiroyuki ; Sakayori, Atsushi ; Kawabata, Keiichi ; Ihara, Yoshinori
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| 2.
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Ihara, Yoshinori ; Uehara, Akira ; Tsuchiya, Ryokichi ; Kyuno, Eishin
概要:
The following six cobalt(III) complexes containing phenylbiguanide were prepared and the thermal reactions were followed
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both isothermally and non-isothermally (derivatographically) in the solid phase: trans-[Co(A)2(phbgH)2]X3·n2O, where A denotes volatile ligands such as NH3, CH3NH2 or C5H5N; phbgH denotes 1-phenylbiguanide, X chloride or bromide ion; and n is 2 or 3. From the electronic, IR and far-IR spectra and magnetic susceptibilities of these complexes before and after heating, the products obtained by evolving volatile ligands were found to be uniform bivalent cobalt complexes without rupture of the bonds of phbgH to cobalt in spite of the reduction of central cobalt(III) ion, except for the complexes containing ammonia. The reaction seems to be caused by the electron transfer from the coordinated phbgH to cobalt, not from the outer-sphere anions.
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| 3.
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Ihara, Yoshinori ; Tsuchiya, Ryokichi
概要:
Thermal reactions of the complexes, [Ni(abi)4]X2·nH2O (abi, 2-aminobenzimidazole; X, Cl, Br, I, NO3, ClO4, or 1/2SO4; n,
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3 for chloride and bromide, 1 for nitrate, and 0 for others) were investigated. Distinct color changes from orange to green were observed in the three complexes of chloride, bromide, and nitrate upon heating. It was found from the changes in absorption and far-IR spectra and magnetic susceptibilities under the thermal reactions that the complexes undergo transformation from square planar to tetragonally distorted octahedral structures, involving an increase in the coordination number from four to six. No such transformation could be found in the corresponding iodide, perchlorate, and sulfate. The effect of the introduced amino group on the structural conversion reactions of the abi complexes is discussed as compared with the corresponding benzimidazole complexes, [Ni(bimd)4]X2, which underwent transformation from square planar to octahedral structure upon heating when X is I or NO3.
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| 4.
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Ihara, Yoshinori ; Izumi, Eiichi ; Uehara, Akira ; Tsuchiya, Ryokichi ; Nakagawa, Shigeo ; Kyuno, Eishin
概要:
Thermal reactions of the [Ni(H2O)2(AA)2]X2·nH2O complexes in a solid phase were investigated, where AA is N,N′-diethylet
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hylenediamine (NN′-deen), N,N-dimethylethylenediamine (NN-dmen), or N,N′-dimethylethylenediamine (NN′-dmen), and where X− is Cl−, Br−, I−, NO3− or ClO4−. By means of thermal analyses and spectral and magnetic measurements in a series of these complexes before and after heating, the following results were obtained. In the case of the NN′-deen complexes, only the perchlorate deaquates to change from octahedral to square-planar, but the other salts, such as the chloride, bromide, iodide, and nitrate, undergo deaquation-anation keeping their octahedral configuration. The deaquation-anation was also observed in the chloride, bromide, and nitrate of the NN-dmen complexes, but the iodide deaquated, and so was transformed from octahedral to square-planar. In the NN′-dmen complexes, only deaquation-anation was detected, irrespective of the anions (Cl−, Br−, I−, and NO3−). The effects of N-substituents in the diamines and the anions on the above transformation were discussed.
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| 5.
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Ihara, Yoshinori ; Satake, Yasuhiro ; Suzuki, Masatatsu ; Uehara, Akira
概要:
The thermochemical changes in coordination structure of diaquabis(N,N- or N,N′,-dialkylethylenediamine)nickel(II) comple
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xes ([Ni(H2O)2(diamine)2]X2·nH2O) were reinvestigated by means of TG-DTA and electronic spectroscopy at room and elevated temperatures, where diamine is N,N (or N,N′-dimethylethylenediamine (NN- or NN′-dmen) or N,N-(or N,N′)-diethylethylenediamine (NN- or NN′-deen); X is Cl−, Br−, I−, or NO3−; n is 0, 1, 2, or 3. The diaqua complexes prepared were all trans except for cis-[Ni(H2O)2(NN-dmen)2]I2. The trans complexes with the symmetric (N,N′-dialkylsubstituted) diamines brought about a deaquation-anation upon heating, retaining the original trans configuration, while those with the asymmetric (N,N-dialkylsubstituted) diamines transformed into the cis complexes. In the case of the NN-dmen complexes, cis-halogenoaqua species were isolated as a stable intermediate during the thermal reactions. The complex nitrates changed to trans-dinitrato or cis-mononitrato species depending upon the diamines. The effects of the N-substituents in the diamines and of the anions on the patterns of thermal reactions were also discussed.
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| 6.
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Ihara, Yoshinori ; Sakino, Tomomi ; Ishikawa, Mieko ; Koyata, Takanori
概要:
The solid-phase thermal reactions of trans-diaquabis(diamine)nickel(II) complexes (trans-[Ni(diamine)2(H2O)2]X2) were in
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vestigated by means of TG/DTA and DSC, and high-temperature electronic spectrometry, where the diamine is an optically active diamine such as (1S,2S)-1,2-diphenyl-1,2-ethanediamine or (S)-4-methyl-1,2-pentanediamine, and X is Cl−, Br−, or NO3−. Several complexes were peculiarly transformed into cis-[NiX2(diamine)2] upon thermal deaquation-anation, and then isomerized to trans-[NiX2(diamine)2] upon further heating. The results were in contrast to the reactions of the complexes with the corresponding racemic diamines which underwent a simple deaquation-anation, retaining an original trans configuration. The differences must come from a slight difference in the conformation of diamine ligands between trans-[Ni(R-diamine)(S-diamine)(H2O)2]X2 which is obtained for the rac-diamines and trans-[Ni(R- or S-diamine)2(H2O)2]X2 which is obtained for the optically active diamines.
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| 7.
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Ihara, Yoshinori
概要:
Nickel(II) complexes [Ni(phenen)2](ClO4)2 and [Ni(H2O)2(phenen)2]X2 (phenen=1-phenyl-1,2-ethanediamine, X=Cl, Br, or NO3
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) were prepared, and their thermal behavior was investigated in the solid phase. The nitrate showed a thermochromism consisting of two steps, violet→yellow→violet, which corresponds to a structural change from an octahedral diaqua complex to a square planar anhydride, and then to the octahedral dinitrato complex, respectively. Both the chloride and bromide were converted into the octahedral dianiono complexes by thermal deaquation-anation, retaining their octahedral configuration. However, no change was observed in the perchlorate, which is invariably square planar.
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| 8.
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Ihara, Yoshinori ; Tsuchiya, Ryokichi
概要:
The following ten nickel(II) complexes with meso- or dl-1,2-diphenyl-1,2-ethanediamine (abbreviated as meso-stien and dl-stien, respectively) were prepared, and their thermal behavior was investigated in the
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solid phase: [Ni(meso-stien)2]X2 (X=Cl, Br, I, NO3, or ClO4), [Ni(dl-stien)2]X2 (X=I or ClO4), and [Ni(H2O)2(dl-stien)2]X2 (X=Cl, Br, or NO3). The square planar bis(dl-stien) complex chloride, bromide, and nitrate obtained by thermal dehydration of their respective octahedral diaqua complexes were found by various techniques to be transformed, upon further heating, to the octahedral diacido bis(dl-stien) complexes. The complexes containing dl-stien have a stronger tendency to show such structural transformations than those containing meso-stien. The reason for this difference is discussed.
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| 9.
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Ihara, Yoshinori ; Fukuda, Yutaka ; Sone, Kozo
概要:
Ten octahedral anionobis(C-substituted ethylenediamine)nickel(II) complexes were obtained by thermal reactions of corresponding diaqua salts, and their electronic and IR spectra were examined to see whether they are cis or trans.
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Most of them were found to be trans, but [Ni(NO3)(m-bn)2](NO3) and [NiCl2(i-bn)2] were cis.
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| 10.
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Ihara, Yoshinori ; Wada, Akiko ; Fukuda, Yutaka ; Sone, Kozo
概要:
Nickel(II) complexes of 1,2-butanediamine(1,2-bn) and 3,3-dimethyl-1,2-butanediamine(dmbn), were prepared, and their the
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rmal behavior was investigated in solid phase. The original complexes were all violet, octahedral diaquabis(diamine) complexes([Ni(H2O)2(1,2-bn/dmbn)2]X2; X=Cl, Br, NO3, or ClO4). The 1,2-bn complexes with Cl− or Br− and the dmbn complex with NO3− showed a two-step thermochromism, violet→yellow→violet blue, upon heating. These steps correspond to structural changes to a square planar anhydride, and then to an octahedral dianiono complex. The complexes of both ligands with ClO4− underwent only thermal deaquation, changing into orange square planar anhydride. Other salts, the 1,2-bn complex with NO3− and the dmbn complexes with Cl− or Br−, were converted into octahedral dianiono complexes by thermal deaquation-anation which occurs in one step. The differences among the thermal reactivities of the complexes with different diamines can be understood on the basis of steric hindrance caused by the substituent groups on the diamine.
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