2003 Fiscal Year Annual Research Report

配位原子への水素結合による金属錯体の反応制御

Research Project

Project/Area Number	12304040
Research Institution	Osaka University
Principal Investigator	上山憲一大阪大学, 大学院・理学研究科, 教授 (80093376)
Co-Investigator(Kenkyū-buntansha)	岡村高明大阪大学, 大学院・理学研究科, 助手 (90252569) 山本仁大阪大学, 大学院・理学研究科, 助教授 (20222383)
Keywords	ポリ(カルボキシラート) / バイオミネラル / 炭酸カルシウム / カルシウム錯体 / 脱プロトン化 / 水素結合 / pK_a / 結晶形態
Research Abstract	分子内NH【triple bond】O水素結合を持つ種々の高分子配位子、ポリ(カルボキシラート)、を用いて、バイオミネラルのモデルの炭酸カルシウム結晶複合体を合成し、得られた複合体に対して種々の測定を行って、高分子配位子の結合や結晶形態について調べた。その結果、分子内NH【triple bond】O水素結合を形成する配位子は多くの場合、強くCaCO_3結晶に結合していることが明らかとなった。カルボキシル基の脱プロトン化過程において、基底状態であるカルボン酸の-OH酸素原子に対しては近傍のアミド基からの水素結合形成はないが、遷移状態においてNH【triple bond】O水素結合が形成される。このため、脱プロトン化過程のエネルギー障壁が減少し、結果としてpK_aが低下する。このpK_aのシフトにより、カルボキシレート酸素原子の塩基性が減少し、Ca-O結合が加水分解を受けにくくなる。Ca^<2+>との錯形成定数が増大し、故に強固なCa-O結合が形成される。水素結合形成のアミド基で嵩高くなった配位子が、Ca^<2+>と中性の錯体を形成する時、Ca-O結合が共有結合性を示す。これはCa-O結合におけるCaのd_<yz>軌道と酸素原子のp_z軌道の相互作用により、この共有結合性もCa-O結合を強固なものとしている。実際、NH【triple bond】O水素結合を形成する安息香酸誘導体のカルシウム錯体では、一般的なCa錯体に比べて短いCa-O結合となる。この様な水素結合の寄与は、水素結合を形成しないポリ(アクリル酸)が洗浄により結晶より容易に解離することと比較しても明らかである。また、NH【triple bond】O水素結合の強さとCaCO_3結晶の晶形とを比較すると、水素結合が強い場合には、CaCO_3の結晶成長が制御され、準安定相の結晶が得られ、逆に水素結合が弱い場合には、配位子非存在下と同様、最安定相の結晶が得られる。

Research Products

(24 results)

All Other

All Publications (24 results)

[Publications] K.Takahashi, M.Doi, A.Kobayashi, T.Taguchi, A.Onoda, T.Okamura, H.Yamamoto, N.Ueyama: "Formation of 6-,7- or 8-membered ring intraside-chain NHO hydrogen bond toward Ca-binding oxyanion in Poly(allylaminocarboxylate) ligands stabilizes CaCO_3 vaterite crystals"J.Cryst.Growth. 263・1-4. 552-563 (2004)
[Publications] K.Takahashi, M.Doi, A.Kobayashi, T.Taguchi, A.Onoda, T.Okamura, H.Yamamoto, N.Ueyama: "Direct Observation of Polymer-Binding Site on Calcite Crystal by FE/SEM : Regulation of Binding Abilities by a Rotation of Amide Group in Poly(carboxylate) to CaCO_3 Crystals"Chem.Lett.. 33・2. 192-193 (2004)
[Publications] K.Takahashi, T.Okamura, H.Yamamoto, N.Ueyama: "5-(tert-Butylamino)-5-oxopentanoic acid"Acta Cryst.. E60. o19-o21 (2004)
[Publications] X.M.Ouyang, Z.-W.Li, T.-a.Okamura, Y.Z.Li, W.Y.Sun, W.-X.Tang, N.Ueyama: "Construction of metal-organic frameworks through coordination and hydrogen bonding interactions : Syntheses, structures and photoluminescent properties of metal complexes with macrocyclic ligand"J.Solid State Chem.. 177・1. 350-360 (2004)
[Publications] H.-F.Zhu, L.Li, T.Okamura, W.Zhao, W.-Y.Sun, N.Ueyama: "Syntheses, Structures and Photoluminescence Properties of Ag(I), Cu(II), Zn(II) and Mn(II) Complexes with N,N'-Bis(3-pyridylmethyl)-1,4-benzenedimethyleneimine"Bull.Chem.Soc.Jpn. 76・4. 761-767 (2003)
[Publications] H.-F.Zhu, W.-Y.Sun, T.Okamura, N.Ueyama: "Hydrothermal synthesis and structural characterization of one-dimensional coordinate polymers of cobalt(II) and nickel(II) with 1,3,5-benzenetriacetic acid"Inorg.Chem.Commun.. 6・2. 168-173 (2003)
[Publications] W.Zhao, H.F.Zhu, T.A.Okamura, W.Y.Sun, N.Ueyama: "Synthesis and crystal structure of blue luminescent cadmium(II) coordination networks with 4,4'-bis(imidazol-1-ylmethyl)biphenyl from different solvent systems"Supramol.Chem.. 15・5. 345-352 (2003)
[Publications] Y.Wang, X.-M.Ouyang, T.-a.Okamura, W.-Y.Sun, N.Ueyama: "Syntheses and structures of two photofluorescent infinite one-dimensional chains from assembly of tetradentate dipyridyl ligand with cadmium(II) and silver(I) salts"Inorg.Chim.Acta. 353. 68-74 (2003)
[Publications] S.-Y.Wan, Y.-Z.Li, T.Okamura, J.Fan, W.-Y.Sun, N.Ueyama: "Syntheses, Structures, and Properties of Two-Dimensional Honeycomb Networks from the Assembly of the Tripodal Ligand 2,4,6-Tris[4-(imidazol-1-ylmethyl)phenyl]-1,3,5-triazine with Metal Salts"Eur.J.Inorg.Chem.. 20. 3783-3789 (2003)
[Publications] N.Ueyama, K.Takahashi, A.Onoda, T.Okamura, H.Yamamoto: "Conformational switching between carboxylic acid and carboxylate anion states by NH center dot center dot center dot O hydrogen bonding"Macromol.Symp.. 204. 287-294 (2003)
[Publications] S.Takamizawa, E.-i.Nakata, T.Saito, T.-a.Okamura, N.Ueyama: "Microporous solid based solely upon an intermolecular NH 【triple bond】 O and NH 【triple bond】 Cl hydrogen bond network"Inorg.Chem.Commun.. 6・9. 1239-1242 (2003)
[Publications] K.Takahashi, T.Okamura, H.Yamamoto, N.Ueyama: "A 1:1 diastereoisomeric complex of trans-2-{[(R)-(+)-1-phenylethylamino]-carbonyl}-cyclohexanecarboxylic acid"Acta Cryst.. E59. o1953-o1955 (2003)
[Publications] X.-M.Ouyang, D.-J.Liu, T.Okamura, H.-W.Bu, W.-Y.Sun, W.-X.Tang, N.Ueyama: "Syntheses, structures and photoluminescent properties of cadmium(II), silver(I) and copper(I) complexes with novel long chain tetradentate ligands"Dalton Trans.. 9. 1836-1845 (2003)
[Publications] X.-M.Ouyang, B.-L.Fei, T.Okamura, H.-W.Bu, W.-Y.Sun, W.-X.Tang, N.Ueyama: "Synthesis, Crystal Structures, and Properties of Four Two-Dimensional Network Complexes with Multidentate Bis(Schiff Base) Ligands"Eur.J.Inorg.Chem.. 4. 618-627 (2003)
[Publications] A.Onoda, T.Okamura, H.Yamamoto, N.Ueyama: "2,6-Bis(triphenylacetylamino)phenol"Acta Cryst.. E59. o1202-o1204 (2003)
[Publications] A.Onoda, K.Kawakita, T.Okamura, H.Yamamoto, N.Ueyama: "A distorted square-planar Pd^<II> complex with a shortened Pd-Cl bond induced by the bulky terpyridyl ligand 6,6"-dimesityl-2,2':6',2"-terpyridine"Acta Cryst.. E59. m291-m293 (2003)
[Publications] A.Onoda, K.Kawakita, T.Okamura, H.Yamamoto, N.Ueyama: "(Acetonitrile)(6,6"-dimesityl-2,2':6',2"-terpyridine)copper(I) hexafluorophosphate"Acta Cryst.. E59. m266-m267 (2003)
[Publications] J.Fan, H.-F.Zhu, T.Okamura, W.-Y.Sun, W.-X.Tang, N.Ueyama: "Three-dimensional photoluminescent pillared metal-organic framework with 4.82 topological channels obtained from the assembly of cadmium(II) acetate and trimellitic salts"New J.Chem.. 27・10. 1409-1411 (2003)
[Publications] J.Fan, H.-F.Zhu, T.Okamura, W.-Y.Sun, W.-X.Tang, N.Ueyama: "Discrete and Infinite Cage-Like Frameworks with Inclusion of Anionic and Neutral Dpecies and with Intertenetration Phenomena"Chem.Eur.J. 9・19. 4724-4731 (2003)
[Publications] J.Fan, M.-H.Shu, T.Okamura, Y.-Z.Li, W.-Y Sun, W.-X.Tang, N.Ueyama: "Solvent effect on the structure and topology of metal-orgainc frameworks with the rigid tripodal star ligand 1,3,5-tris(1-imidazoyl)banzene and lead(II) nitrate"New J.Chem.. 27・9. 1307-1309 (2003)
[Publications] J.Fan, W.Y.Sun, T.Okamura, W.X.Tang, N.Ueyama: "Novel metal-organic frameworks with specific topology from new tripodal ligands : 1,3,5-tris(1-imidazolyl)benzene and 1,3-bis(1-imidazolyl)-5-(imidazol-1-ylmethyl)benzen"Inorg.Chem.. 42・10. 3168-3175 (2003)
[Publications] J.Fan, H.-F.Zhu, T.Okamura, W.-Y.Sun W.-X.Tang, N.Ueyama: "Novel One-Dimensional Tubelike and Two-Dimensional Polycatenated Metal-Organic Frameworks"Inorg.Chem.. 42・1. 158-162 (2003)
[Publications] T.Okamura, N.Ueyama: "Comprehensive Coordination Chemistry II (全10巻の中、第4巻4.8 Tungstenの章を執筆)"Elsevier Ltd.(Ed.by J.A.McCleverty and T.J.Meyer). 866(529-573) (2004)
[Publications] 上山憲一: "ミネラルの事典 (必須微量金属モリブデンの章を執筆)"朝倉書店(糸川嘉則編). 694(311-317) (2003)

2003 Fiscal Year Annual Research Report

配位原子への水素結合による金属錯体の反応制御

Principal Investigator

上山 憲一 大阪大学, 大学院・理学研究科, 教授 (80093376)

Research Products

[Publications] K.Takahashi, T.Okamura, H.Yamamoto, N.Ueyama: "5-(tert-Butylamino)-5-oxopentanoic acid"Acta Cryst.. E60. o19-o21 (2004)

[Publications] H.-F.Zhu, L.Li, T.Okamura, W.Zhao, W.-Y.Sun, N.Ueyama: "Syntheses, Structures and Photoluminescence Properties of Ag(I), Cu(II), Zn(II) and Mn(II) Complexes with N,N'-Bis(3-pyridylmethyl)-1,4-benzenedimethyleneimine"Bull.Chem.Soc.Jpn. 76・4. 761-767 (2003)

[Publications] H.-F.Zhu, W.-Y.Sun, T.Okamura, N.Ueyama: "Hydrothermal synthesis and structural characterization of one-dimensional coordinate polymers of cobalt(II) and nickel(II) with 1,3,5-benzenetriacetic acid"Inorg.Chem.Commun.. 6・2. 168-173 (2003)

[Publications] W.Zhao, H.F.Zhu, T.A.Okamura, W.Y.Sun, N.Ueyama: "Synthesis and crystal structure of blue luminescent cadmium(II) coordination networks with 4,4'-bis(imidazol-1-ylmethyl)biphenyl from different solvent systems"Supramol.Chem.. 15・5. 345-352 (2003)

[Publications] Y.Wang, X.-M.Ouyang, T.-a.Okamura, W.-Y.Sun, N.Ueyama: "Syntheses and structures of two photofluorescent infinite one-dimensional chains from assembly of tetradentate dipyridyl ligand with cadmium(II) and silver(I) salts"Inorg.Chim.Acta. 353. 68-74 (2003)

[Publications] N.Ueyama, K.Takahashi, A.Onoda, T.Okamura, H.Yamamoto: "Conformational switching between carboxylic acid and carboxylate anion states by NH center dot center dot center dot O hydrogen bonding"Macromol.Symp.. 204. 287-294 (2003)

[Publications] S.Takamizawa, E.-i.Nakata, T.Saito, T.-a.Okamura, N.Ueyama: "Microporous solid based solely upon an intermolecular NH 【triple bond】 O and NH 【triple bond】 Cl hydrogen bond network"Inorg.Chem.Commun.. 6・9. 1239-1242 (2003)

[Publications] K.Takahashi, T.Okamura, H.Yamamoto, N.Ueyama: "A 1:1 diastereoisomeric complex of trans-2-{[(R)-(+)-1-phenylethylamino]-carbonyl}-cyclohexanecarboxylic acid"Acta Cryst.. E59. o1953-o1955 (2003)

[Publications] X.-M.Ouyang, D.-J.Liu, T.Okamura, H.-W.Bu, W.-Y.Sun, W.-X.Tang, N.Ueyama: "Syntheses, structures and photoluminescent properties of cadmium(II), silver(I) and copper(I) complexes with novel long chain tetradentate ligands"Dalton Trans.. 9. 1836-1845 (2003)

[Publications] X.-M.Ouyang, B.-L.Fei, T.Okamura, H.-W.Bu, W.-Y.Sun, W.-X.Tang, N.Ueyama: "Synthesis, Crystal Structures, and Properties of Four Two-Dimensional Network Complexes with Multidentate Bis(Schiff Base) Ligands"Eur.J.Inorg.Chem.. 4. 618-627 (2003)

[Publications] A.Onoda, T.Okamura, H.Yamamoto, N.Ueyama: "2,6-Bis(triphenylacetylamino)phenol"Acta Cryst.. E59. o1202-o1204 (2003)

[Publications] A.Onoda, K.Kawakita, T.Okamura, H.Yamamoto, N.Ueyama: "A distorted square-planar Pd^<II> complex with a shortened Pd-Cl bond induced by the bulky terpyridyl ligand 6,6"-dimesityl-2,2':6',2"-terpyridine"Acta Cryst.. E59. m291-m293 (2003)

[Publications] A.Onoda, K.Kawakita, T.Okamura, H.Yamamoto, N.Ueyama: "(Acetonitrile)(6,6"-dimesityl-2,2':6',2"-terpyridine)copper(I) hexafluorophosphate"Acta Cryst.. E59. m266-m267 (2003)

[Publications] J.Fan, H.-F.Zhu, T.Okamura, W.-Y.Sun, W.-X.Tang, N.Ueyama: "Three-dimensional photoluminescent pillared metal-organic framework with 4.82 topological channels obtained from the assembly of cadmium(II) acetate and trimellitic salts"New J.Chem.. 27・10. 1409-1411 (2003)

[Publications] J.Fan, H.-F.Zhu, T.Okamura, W.-Y.Sun, W.-X.Tang, N.Ueyama: "Discrete and Infinite Cage-Like Frameworks with Inclusion of Anionic and Neutral Dpecies and with Intertenetration Phenomena"Chem.Eur.J. 9・19. 4724-4731 (2003)

[Publications] J.Fan, M.-H.Shu, T.Okamura, Y.-Z.Li, W.-Y Sun, W.-X.Tang, N.Ueyama: "Solvent effect on the structure and topology of metal-orgainc frameworks with the rigid tripodal star ligand 1,3,5-tris(1-imidazoyl)banzene and lead(II) nitrate"New J.Chem.. 27・9. 1307-1309 (2003)

[Publications] J.Fan, W.Y.Sun, T.Okamura, W.X.Tang, N.Ueyama: "Novel metal-organic frameworks with specific topology from new tripodal ligands : 1,3,5-tris(1-imidazolyl)benzene and 1,3-bis(1-imidazolyl)-5-(imidazol-1-ylmethyl)benzen"Inorg.Chem.. 42・10. 3168-3175 (2003)

[Publications] J.Fan, H.-F.Zhu, T.Okamura, W.-Y.Sun W.-X.Tang, N.Ueyama: "Novel One-Dimensional Tubelike and Two-Dimensional Polycatenated Metal-Organic Frameworks"Inorg.Chem.. 42・1. 158-162 (2003)

[Publications] T.Okamura, N.Ueyama: "Comprehensive Coordination Chemistry II (全10巻の中、第4巻4.8 Tungstenの章を執筆)"Elsevier Ltd.(Ed.by J.A.McCleverty and T.J.Meyer). 866(529-573) (2004)

[Publications] 上山憲一: "ミネラルの事典 (必須微量金属モリブデンの章を執筆)"朝倉書店(糸川嘉則 編). 694(311-317) (2003)

上山憲一大阪大学, 大学院・理学研究科, 教授 (80093376)

[Publications] 上山憲一: "ミネラルの事典 (必須微量金属モリブデンの章を執筆)"朝倉書店(糸川嘉則編). 694(311-317) (2003)