Structures and functions of novel organometallic coordination polymers constructed by metal ions and aromatic compounds

金属离子与芳香族化合物构建的新型有机金属配位聚合物的结构与功能

• 批准号: 14540522
• 负责人: MAEKAWA Masahiko
• 金额: $ 1.79万
• 依托单位: Kinki University
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for Scientific Research (C)
• 财政年份: 2002
• 资助国家: 日本
• 起止时间: 2002 至 2003
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/grant/KAKENHI-PROJECT-14540522/
• 关键词: Rhodium Complexes; Indium Complexes 1; Crystal Structures; Paracyclophane Complexes; Terphenyl Complexes 1; Cyclopentadienyl Complexes; Cyclooctadiene Complexes; Coordination polymers; X線結晶構造; 核磁気共鳴; 配位高分子錯体; シクロペンタジニエル錯体; ジエン錯体

We systematically prepared nine[2.2]paracyclophane complexes of Rh and Ir,[Rh(η^6-pcp)(C_2H_4)_2]BF_4・thf 1・thf (pcp=[2.2]paracyclophane),[Rh(η^6-pcp)(diene)]BF_4 (diene=1,5-cyclooctadiene (cod) 2・CH_2Cl_2;2,5-norbornadiene (nbd) 3),[Rh2(η^6,η^6-pcp)(diene)_2](BF_4)_2 (diene=cod 4;nbd 5),[Ir(η^6-pcp)(cod)]X (X=BF_4 6a;ClO_4 6b・CH_2Cl_2) and [Ir2(η^6,η^6-pcp)(cod)_2]X_2 (X=BF_4 7a;ClO_4 7b), seven structures of which were crystallographically characterized. In complexes 1・thf,2・CH_2Cl_2,3 and 6b・CH_2Cl_2, each of the Rh or Ir atoms are η^6-bonded to the upper side of the two decks in the pep ligand to afford a mononuclear structure. The average interannular distances between the two decks are 3.03(1・thf),3.01 (2・CH_2Cl_2),3.04 (3)and 3.01 Å(6b・CH2Cl2), respectively. In complexes 4,5 and 7b, two Rh or Ir atoms are η^6-coordinated to the upper and lower decks in the pep ligand to provide a dinuclear structure. The average interannular distances between the two decks are 3.04(4),3.05(5)and … More 3.05 Å (7b),respectively. On complexes 1・thf-7b, the average interannular distances of 3.01 to 3.05 Å between the two decks were found to be shorter than that(3.09 Å) of the metal-free pep ligand, suggesting that the repulsive π-interaction between the two decks is reduced by the coordination of the metal fragment with the diene ligand to the pep ligand. In addition, the relationships between the intramolecular distances and the configuration of the two ethylenic bridges were quite obvious. If the interannular distance was shorter than 3.05 Å, the configuration of the two ethylenic bridges was more likely a twisted cross type, and if the interannular distance was shorter than 3.01 Å, the configuration was more likely a parallel type, accompanying with the structure conversion of the two ethylenic bridges and the slide of the two decks.Novel two indium terphenyl complexes were also prepared and their structures were characterized crystallographically. The reaction of [Ir(cod)_2]BF_4 with p-terphenyl(p-tp) in CH_2Cl_2 to afford dinuclear Ir(I) complex {[Ir_2(p-tp)(cod)_2](BF_4)_2・2CH_2Cl_2}_3(8・2CH_2Cl_2), whereas the reaction of the intermediate [Ir(η5-C_5Me_5)(M_2CO)_3]^<3+> in Me_2CO with m-terphenyl(m-tp) to provide mononuclear Ir(III) complex [Ir(m-tp)(η^5-C_5Me_5)](BF_4)_2 (9).In complex 8・2CH_2Cl_2 two Ir atoms are η^6-coordinated to both sides of terminal benzene rings from the upper and lower sides in the p-tp ligand, while one Ir atom is η^6-coordinated to one side of the terminal benzene ring in the m-tp ligand in complex 9.Each crystal structure described the first coordination mode found in metal complexes with the m-and p-tp ligands. Less

我们系统地制备了9个Rh和Ir的[2.2]对环己烷配合物，[Rh(η^6-pcp)(C_2H_4)_2]BF_4·thf 1·thf （pcp=[2.2]对环己烷），[Rh(η^6-pcp)（二烯）]BF_4(二烯=1,5-环己烷（cod） 2·CH_2Cl_2；2,5-降冰片二烯（nbd） 3)、[Rh2(η^6,η^6-pcp)(diene)_2](BF_4)_2 （diene=cod 4;nbd 5）、[Ir(η^6-pcp)(cod)]X （X=BF_4 6a;ClO_4 6b·CH_2Cl_2）和[Ir2(η^6,η^6-pcp)(cod)_2]X_2 (X=BF_4 7a;ClO_4 7b)，对其中7种结构进行了晶体学表征。在配合物1·thf，2·CH_2Cl_2,3和6b·CH_2Cl_2中，每个Rh或Ir原子都与pep配体中两层的上部成η^6键，形成单核结构。两层甲板间的平均环间距离分别为3.03（1·thf）、3.01（2·CH_2Cl_2）、3.04(3)和3.01 Å（6b·CH2Cl2）。在配合物4,5和7b中，两个Rh或Ir原子以η^6配位在pep配体的上下甲板上，形成双核结构。两层甲板间的平均环间距离分别为3.04(4)、3.05(5)和…More 3.05 Å （7b）。在配合物1·thf-7b上，两层间的平均环间距为3.01 ~ 3.05 Å，小于无金属pep配体的平均环间距（3.09 Å），表明金属碎片与二烯配体配位到pep配体上，降低了两层间的排斥π相互作用。此外，分子内距离与两个乙烯桥的构型之间的关系非常明显。当环间距离小于3.05 Å时，两座乙烯桥的构型更有可能是扭十字型，当环间距离小于3.01 Å时，构型更有可能是平行型，并伴随着两座乙烯桥的结构转换和两层甲板的滑动。制备了两种新型的三苯基铟配合物，并对其结构进行了晶体学表征。[Ir(cod)_2]BF_4在CH_2Cl_2中与对三苯基（p-tp）反应生成双核Ir(I)配合物{[Ir_2(p-tp)(cod)_2](BF_4)_2·2CH_2Cl_2}_3(8·2CH_2Cl_2)，而中间体[Ir(η5-C_5Me_5)(M_2CO)_3]^<3+>在Me_2CO中与间三苯基（m-tp）反应生成单核Ir（III）配合物[Ir(m-tp)(η^5-C_5Me_5)](BF_4)_2(9)。在配合物8·2CH_2Cl_2中，两个Ir原子从p-tp配体的上下两侧的末端苯环上η^6配位，而在配合物9中，一个Ir原子在m-tp配体的末端苯环上η^6配位。每种晶体结构都描述了与m和p-tp配体在金属配合物中发现的第一种配位模式。少

项目成果

M.Maekawa, et al.: "Crystal structure of tri-μ-chloro-bis[(1,2,3,4,5-η)-1,2,3,4,5-pentamethyl-2,4-cyclopentadien-1-yl)]-diiridium tetrafluoroborate with a unique trigonal-bipyramidal Ir_2Cl_3 core"Analytical Science. 20. X11-X12 (2004)

M. Maekawa 等人：“三-μ-氯-双[(1,2,3,4,5-η)-1,2,3,4,5-五甲基-2,4-的晶体结构”具有独特三角双锥 Ir_2Cl_3 核的环戊二烯-1-基)]-四氟硼酸二铱”分析科学. 20. X11-X12 (2004)

M.Maekawa, N.Hashimoto, T.Kuroda-Sowa, Y.Suenaga, M.Munakata: "Syntheses and Crystal Structures of Mononuclear[2.2]Paracyclophane Complexes of Rhodium and Iridium Supported by the Pentamethyl-cyclopentadienyl Ligand.[M(η^6-pcp)( η^5-C_5Me_5)](BF_4)_2 (M=R

M.Maekawa、N.Hashimoto、T.Kuroda-Sowa、Y.Suenaga、M.Munakata：“五甲基环戊二烯基配体支持的铑和铱单核[2.2]对环芳烷配合物的合成和晶体结构。[M(η) ^6-pcp)( η^5-C_5Me_5)](BF_4)_2 (M=R

M.Maekawa, et al.: "Syntheses and crystal structures of the first iridium complexes with m- and p-terphenyl(tp).{[Ir_2(p-tp)(cod)_2](BF_4)_2・2CH_2Cl_2}_3 and[Ir(m-tp)(η^5-C_5Me_5)](BF_4)_2"Inorganica Chimica Acta. 357. 331-338 (2004)

M. Maekawa 等人：“第一个铱与间三联苯和对三联苯(tp)的配合物的合成和晶体结构。{[Ir_2(p-tp)(cod)_2](BF_4)_2·2CH_2Cl_2}_3和[Ir(m-tp)(η^5-C_5Me_5)](BF_4)_2《无机化学学报》. 357. 331-338 (2004)

M.Maekawa, et al.: "Tris(solvent) iridium complex spported by the η^5-pentamethylcyclopentadienyl ligand. Refinement of [Ir(η^5-C_5Me_5)(Me_2CO)_2(H_2O〕](BF_4)_2"近畿大学理工学総合研究所研究報告. 16. 21-24 (2004)

M. Maekawa, et al.：“由 η^5-五甲基环戊二烯基配体支持的 Tris（溶剂）铱络合物。[Ir(η^5-C_5Me_5)(Me_2CO)_2(H_2O]](BF_4)_2 的精制”Kinki大学科学与工程研究院研究报告。 16. 21-24 (2004)

M.Maekawa, et al.: "Tris(solvent)iridium complex supported by the η^5-penta-methylcyclopentadienyl ligand. Refinement of [Ir(η^5-C_5Me_5)(Me_2CO)_2(H_2O)](BF_4)_2"近畿大学理工学総合研究所研究報告. 21. 21-24 (2004)

M. Maekawa 等人：“由 η^5-五甲基环戊二烯基配体支持的三（溶剂）铱络合物。[Ir(η^5-C_5Me_5)(Me_2CO)_2(H_2O)](BF_4)_2 的精制《近畿大学科学技术研究所研究报告》. 21. 21-24 (2004)