有貴金属共役系の構築と物性への展開

1995 Fiscal Year Annual Research Report

• Project/Area Number: 06101004
• Research Institution: Osaka University
• Principal Investigator: 中村 彰 大阪大学, 理学部, 教授 (80029404)
• Co-Investigator(Kenkyū-buntansha): 岡村 高明 大阪大学, 理学部, 助手 (90252569) ; 中野 雅由 大阪大学, 理学部, 助手 (80252568) ; 武田 定 大阪大学, 理学部, 助手 (00155011) ; 森 和亮 大阪大学, 理学部, 助教授 (60029709) ; 山口 兆 大阪大学, 理学部, 教授 (80029537)
• Keywords: 有機金属共役系 / 金属-金属多重結合 / 水素結合 / 磁性 / 固体NMR / 分子軌道計算 / 非線形光学 / シクロペンタジェニル

Research Abstract

1.直線状多核錯体としてPtMoMoPt四核が架橋型有機リガンドでポリマー化した全く新しい型の有機金属共役系を合成し、光学特性を調べ、高い第三非線形定数を持つことを見出した。
特にPt-Ce-Cr-Ptについては、X線解析の他磁気測定や固体NMRスペクトルなどの結果やさらには量子化学計算による解析の結果、金属間磁気相互作用や金属間結合の特徴を明らかにした。
2.共役ポリエン系と金属'Zr,Ru)との結合については、これまでに未知の低温固相での結合状態変化を固体高分解能NMRスペクトル測定によって見いだした。
3.フマル酸やテレフタル酸など有機p共役性をもつジカルボン酸を配位子としMo-Mo金属間結合をもつ新規多次元錯体を合成した。またこれら新規錯体が色々な気体を可逆的に吸蔵放出することを見いだし、これに伴う局所構造変化を固体NMRスペクトルにより見いだした。。
4.昨年度に開発した非線形光学過程の計算、解析法を用いて、金属-メチレン系の3次超分極率γを計算した。電子相関依存性が大きく、また、電子配置によるγの絶対値、符号の顕著な変化が認められた。
5.Cuのカルボキシラート二核錯体を合成しNH-O水素結合を通じた磁気的相互作用があることを見出しその指標である-2J値がこれまでにない大きな値であることを明らかにした。
6.新規ランタノイド-アレーンチオラート錯体の系統的合成法を開発した。これらの錯体を触媒とするメチルメタクリレートの重合を検討し、HMPA-ランタニドpπ-dπ相互作用によってシンジオタクチック特異的重合に制御できることを見いだした。

Research Products

• [Publications] H.Kawaguchi,K.Tatsumi,A.Nakamura: "A Zigzag Chain Structure of a 3-Thiapentane-1,5-dithiolato Vanadium Complex linked by Lithium ions" J.Chem.Soc.,Chem.Commun.1995. 111-112 (1995)
• [Publications] W.-Y.Sun,T.Ueno,N.Ueyama,A.Nakamura: "^<19>F NMR Investigations of Cobalt(II)Complexes with Cysteine-Containing Peptide Ligands" Magnetic Resonance in Chemistry. 33. 174-177 (1995)
• [Publications] H.Zaima,N.Ueyama,H.Adachi,A.Nakamura: "^1H,^<13>C,and^<113>Cd-NMR Study of the Cd(II)Complex of a Blocked Peptide,Z-Cys-Ala-Pro-His-OMe,in Organic Solvents" Biopolymers. 35. 319-329 (1995)
• [Publications] A.Nakamura: "Organometallic π-Conjugated Systems" Bull.Chem.Soc.Jpn.68. 1515-1521 (1995)
• [Publications] H.Oku,N.Ueyama,A.Nakamura: "Thiolato-Activated Oxo-Metal Bond Features in Molybdenum and Tungsten Oxidoreductase Models As Revealed by Raman Spectroscopy" Inorg.Chem.34. 3667-3676 (1995)
• [Publications] K.Mashima,S.Fujikawa,Y.Tanaka,H.Urata,T.Osiki,E.Tanaka,A.Nakamura: "Living Polymerization of Ethylene Catalyzed by Diene Complexes of Niobium and Tantalum,M(η^5-C_5Me_5)(η^4-diene)X_4 and M(η^5-C_5Me_5)(η^4-diene)_2(M=Nb and Ta),…" Organ ometallecs. 14. 2633-2640 (1995)
• [Publications] N.Ueyama,T.Okamura,Y.Yamada,A.Nakamura: "Crystal and Solution Structures of Novel Bulky Bis〔2,6di(acylamino)phenyl〕Disulfides.Absence of Convalent NH cS Hydrogen Bond between Amide NH and Neighboring Disulfide-" J.Org.Chem. 60. 4893-4899 (1995)
• [Publications] H.Oku,N.Ueyama,A.Nakamura: "Electronic and Steric Effect of Bulky Triphenylsilyl Substituent in the Monooxobenzenedithiolatomolybdenum(V)Complex and the Tungsten Analog as Models of Molybdenum and Tungsten Oxidoreductases" Chem.Lett.1995. 621-622 (1995)
• [Publications] A.Nakamura,K.Mashima: "Recent progress in the chemistry of 1,3-diene complexes of niobium and tantalum" J.Organomet.Chem.500. 261-267 (1995)
• [Publications] K.Mashima,T.Shibahara,Y.Nakayama,A.Nakamura: "Synthesis and characterization of cationic pyridine-2-thiolate complexes of lanthanoid(III):crystal structures of pentagonal bipyramidal[Ln(SC_5H_4N)_2(hmpa)_3]I C" J.Organomet.Chem.501. 263-269 (1995)
• [Publications] K.Mashima,Y.Tanaka,A.Nakamura: "Synthesis,characterization and reactions of ethylene complexes bearing Ta(η^5-C_5R_5)(η^4-buta-1,3-diene)fragments(R=H,Me)" J.Organomet.Chem.502. 19-23 (1995)
• [Publications] T.Daniel,H.Nagao,K.Tanaka,A.Nakamura: "Norbornadiene(bipyridyl)molybdenum(II)Complexes:Synthesis,Structure and Reactivity of[Mo(Co)(C_7H_8)(C_<10>H_6R_2N_2](X=I,Br)" chem.Ber. 128. 1007-1013 (1995)
• [Publications] K.Mashima,Y.Tamaka,A.Nakamura: "Synthesis,characterization,and reactions of a mononuclear tantalum-benzyne complex,Ta(η^5-C_5Me_5)(η^4-C_4H_6)(η^2-C_6H_4)" Organometallics. 14. 5642-5651 (1995)
• [Publications] R.Hahn,A.Nakamura,K.Tanaka,Y.Nakayama: "Synthesis and Molecular Structure of a Pentacoordinated Nickel(II)Complex with a Mixed S_2N_3 Coordination Sphere" Inorg.Chem.34. 6562-6564 (1995)
• [Publications] H.Oku,N.Ueyama,A.Nakamura: "A Comparison between the Structures of Tungstopterin Cofactor in Tungsten Oxidoreductase and Model Complex,cis-Dioxobis(2,3-naphthalenedithiolate)tungsten(VI)in Their O-Atom Transfer Reaction" Chem.Left.31. 31-32 (1996)
• [Publications] M.Kondo,H.Oku,N.Ueyama,A.Nakamura: "Synthesis and Properties of a Nitridomolybdenum(VI)Complex Having Benzenedithiolate Ligands.Effect of the Thiolate on the Actication of the Nitrido Ligand" Bull.Chem.Soc.Jpn.69. 117-123 (1996)
• [Publications] K.Mahima,Y.Nakayama,T.Shibahara,H.Fukumoto,A.Nakamura: "Synthesis of Arenethiolate Complexes of Divalent and Trivalent Lanthanides from Metallic Lanthanides and Diaryl Disulfides:Crystal Structures of [{Yb(hmpa)_3}_2(μ-SPh)_3][SPh]and Ln(sph)_3(hmpa)_3…" Inorg.Chem.35. 93-99 (1996)
• [Publications] N.Yeyama,H.Oku,M.Kondo,T.Okamura,N.Yoshinaga,A.Nakamura: "Trans Influence of Oxo and Dithiolene Coordination in Oxidized Models of Molybdenum Oxidoredactactase:Synthesis,Structures,and Properties of Q_2[Mo^<VI>O_2(1,2-benzenedithiolato)_2](Q=NEt_4,PPh_4)and…" Inorg.Chem.35. 643-650 (1996)
• [Publications] M.Nakano,S.Yamada,K.Yamagauchi: "Theoretical studies on hyperpolarizabilities of nitroxide species I." Syntheticc Metals. 71. 1691-1692 (1995)
• [Publications] Y.Matuzaki,M.Nakano,K.Yamaguchi,K.Tanaka et al.: "Second hyperpolarizabilities of p-conjugated silicon-ring polymers" Syntheticc Metals. 71. 1737-1738 (1995)
• [Publications] M.Nakano,K.Yamaguchi: "Numerical Liouville approach:intensity-dependent transient linear andnonlinear optical susceptibilities" Chem.Phys.Lett.234. 323-329 (1995)
• [Publications] M.Nakano,I.Shigemoto,S.Yamada,K.Yamaguchi: "Size-consistent approach and density analysis of hyperpolarizability:Second hyperpolarizabilities of polymeric systems with and without defects" J.Chem.Phys.103. 4175-4191 (1995)
• [Publications] M.Kitazawa,M.Takahashi,T.Wada,,H.Sasabe,M.Nakano,: "Theoretical evaluation of hyperpolarizability of L-2-pyrrolidone-5-carboxylic acid" Bull.Chem.Soc.Jpn.68. 2215-2224 (1995)
• [Publications] M.Nakano,S.Yamada,I.Shigemoto,and K.Yamaguchi: "Theoretical study on the geometry dependence of the second hyperpolarizability of allyl cation based on the MLA three-type analysis" Chem.Phys.Lett.in press.
• [Publications] M.Nakano,S.Yamada,I.Shigemoto,and K.Yamaguchi: "Dynamic (hyper)polarizability density analysis based on virtual excitation processes:Visuallization of dynamic electron fluctuatabilityof systems under time-depe" Chem.Phys.Lett.(in press).
• [Publications] S.Takeda,T.Inabe,T.Mitani,Y.Maruyanmaand K.Ysmaguchi: "ESR Study on the Charge Transfer Complexes of N-Salicylideneanilines containing NHO Hydrogen bond as aDynamic Function" Synthtic Metals,. 70. 1211-1212 (1995)
• [Publications] K.Yakushi,I.Shirotani,I.I.Khairullin,Y.Nakazawa,K.Kanoda and S.Takeda: "Characterization of Poly-CuPc Sheet Polymers Synthesized under High Pressure" Synthtic Metals,. 71. 2287-2288 (1995)
• [Publications] S.Nagatomo,S.Takeda,H.Tamura and N.Nakamura: "Crystal Structure and Hydrogen Bonding in One-dimensional chains of 4,5-Dicyanoimidazole and 4,5-Dichloro;midazole." Bull.Chem.Soc.Jpn.68. 2783-3789 (1995)
• [Publications] S.Takeda,F.Kondoh,N.Nakamura and K.Yamaguchi: "Proton Tunneling and Local Symmetry of the Hydrogen Bond in Rb3H(SO4)2." Physica B. (in press).
• [Publications] S.Takeda,H.Kataoka,S.Ikeda and K.Yamaguchi: "Rotational Tunneling of Methyl Groups of Sc(CH3COO)3 and Sc(CD3DOO)3." Physica B. (in press).
• [Publications] T.Sekikawa,K.Miyakubo,S.Takeda,and T.Kobayashi: "Charge-transfer Effects in a Strongly Hydrogen-bonded System:Potassium Salt of Acetylenedicarboxylic Acid." J.Phys.Chem.(in press).
• [Publications] H.Nishide,T.Kaneko,S.Toriu.et.al: "π-Conjugated Polyradicals with Poly(Phenylenevinylene)Skeleton and Their Through-Bond and Long-Range Interaction." Mol.Cryst.Liq.Cryst.271. 131-138 (1995)
• [Publications] S.Yamanaka,T.Kawakami,H.Nagao,and K.Yamaguchi: "Theoretical Studies of Spin Populations on Nitronyl Nitroxide,Phenyl Nitrunyl Nitroxide and P-NPNN." Mol.Cryst.Liq.Cryst.271. 19-28 (1995)
• [Publications] T.Kaneko,D.Yamaki,G.Maruta,and K.Yamaguchi,et.al.: "Ferrom,agnetic Spin CouPling of tert-Butylnitroxide Diradicals through a Conjugated Oligo(1,2-phenylenevinylene)-Coupler." Chem.lett.2783-2789 (1995)
• [Publications] H.Nishide,T.Kaneko,T.Nii,K.Katoh,E.Tsuchida,and K.Yamaguchi: "Through-Bond and Long-Range Ferromagnetic Spin Alignment in a π-Conjugated Polyradical with a Poly(phenylenevinylene)Skeleton." J.Am.Chem.Soc.117. 548-549 (1995)
• [Publications] S.Yamanaka,T.Kawakami,S.Yamada,H.Nagao,M.Nakano,K.Yamaguchi: "Theoretical studies of Spin density populations on nitroxide and nitrunylnitroxide derivatives." Chem.Phys.lett.240. 268-277 (1995)
• [Publications] S.Yamanaka,M.Okumura,H.Nagao,K.Yamaguchi.: "CASSCF and CASPT2 calculations of hole-doped amines with triplet carbene groups.Possibilities of high-Tc organic ferrimagnets." Chem.Phys.lett.233. 88-94 (1995)
• [Publications] K.Kawakami,S.Yamanaka,W.Mori,K.Yamaguchi,A.Kajiwara,M.Kamachi: "No-overlap and orientation principle for ferromagnetic interactions between nitroxide group." Chem.Phys.lett.235. 414-421 (1995)
• [Publications] S.Yamanaka,T.Kawakami,M.Okumura,K.Yamaguchi.: "CASSCF and CASPT2 calculations of hole-doped polycarbenes.Possibilities of organic fettomagnetic conductors and metals." Chem.Phys.lett.233. 257-265 (1995)
• [Publications] A.Kagiwara,W.Mori,M.Sorai,K.Yamaguchi,and M.Kamachi: "Magnetic properties of nitroxide radicals as the side group of methacrylate or methacrylamide" Mol.Cryst.Liq.Cryst.272. 67-74 (1995)
• [Publications] T.Kawakami,S.Nakayama,H.Nagao,W.Mori,M.Kamachi,K.Yamaguchi.: "Theoretical approches to molcular magnetsm II:no-overlap andorientation principes for ferromagnetic interactions" Mol.Cryst.Liq,Cryst.272. 117-129 (1995)
• [Publications] M.Fujiwara,W.Mori,K.Yamaguchi.: "Iron-schiff base magnetic polymers.synthesis and characterization" Mol.Cryst.Liq,Cryst.274. 175-178 (1995)
• [Publications] W.Mori,and K.Yamaguchi: "Spin glass behavior of synthetic atacamite Cu2Cl(OH)3" Mol.Cryst.Liq,Cryst.274. 113-118 (1995)
• [Publications] M.Kamachi,A.Kajiwara,W.Mori,snd K.Yamaguchi: "Magnetic behavior of polymers conttaining paramagnetic metalloporphyrins" Mol.Cryst.Liq,Cryst.273. 117-124 (1995)
• [Publications] M.Yamashita,K.Inoue,T.Ohisi,T.Takeuchi,T.Yoshida,and W.Mori: "Low-dimension magnetic system with S=1,2/3,2" Mol.Cryst.Liq,Cryst.274. 25-32 (1995)
• [Publications] H.Tamura,S.Tamaka,G.Matsubayashi,W.Mori: "Crysral structure and magnetic properties of[NMe4]4[Mn2(C3S5)4](C3S52-=4,5-dimercapto-1,3-ditheiole-2-thionate)" Inorg.Chimi.Acta.232. 51-55 (1995)
• [Publications] T.Maikawa,M.Nakano,R.Arakawa,G.Matsubayashi,W.Mori: "Preparation and spectroscopic properties of the [Re2(C3S4Se)5]2-anion complex and electrical conductivities of the oxidized species[C3S4Se2-=1,3-dithiole-2-selone-4,5-dithiolate(2-)]" Z.Naturforsch. 50b. 1748-1752 (1995)
• [Publications] M.Mikuriya,K.Nakadera,T.Tokii,and W.Mori: "Synthesis and characterization of tetranuclear manganese(III)complexes with 2,6-bis(salicylidenaminomethyl)-4-metheylphenol" Bull.Chem.Soc.Jpn.68. 3077-3083 (1995)
• [Publications] S.YNO,T.Inagaki,W.Mori,K.Yamaguchi,I.Kinoshita,et.al.: "A novel tetranuclear iron(III)complex having L-alanine bridges and an unprecedented(Fe4(O2H))core" Chem.lett.61-62 (1996)
• [Publications] M.Fujiwara,S.Takamizawa,W.Mori,and K.Yamaguchi: "Molecular design and synthsis of ferro-and ferri magnetic inorganic polymers and complexes with tetrathiolate ligands" Mol.Cryst.Liq.Cryst.(in press).
• [Publications] D.Yamaki,S.Yamada,G.Maruta,T.Kawakami,W.Mori,and K.Yamaguchi: "Theoretical calculation of effective exchange integrals for one-and two-dimensional poly(phenylenemethylene)systems.Possibilities of organic ferrro-and ferri-magnetic solids" Mol.Cryst.Liq.Cryst.(in press).
• [Publications] G.Maruta,D.Yamaki,W.Mori,K.Yamaguchi,and H.Nishide.: "Theoretical study of effectiveexchange integrals for ferromagnetic phenylenevenilene polymers with nitroxides.Possibilities of organic ferro-or ferri-magnetic solids." Mol.Cryst.Liq.Cryst.(in press).
• [Publications] T.Kawakami,A.Oda,W.Mori,K.Yamaguchi,et.al.: "Theoretical studies of the ferromagnetic intermolecular interaction of p-carboxylate phenyl nitronyl niroxide" Mol.Cryst.Liq.Cryst.(in press).
• [Publications] N.Ueyama,K.Taniuchi,T.Okamura,A.Nakamura,H.Maeka,S.Emura: "Effect of the NH…S Hydrogen Bond on the Nature of Hg-S Bonding in Bis[2-(acylamino)benzenethiolato]mercury(II)and Gis[2,6-bis(acylamino)benzenethiolato]mercury(II)Complexes" Inorg.Chem.(in press).
• [Publications] 中村 昇: "有機金属化学辞典 遷移金属 5.ジルコニウム、ハフニウム" 朝倉書店, 54 (1996)