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

我们在系统上准备了九个[2.2] Rh和Ir复合体，[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= cod4; nbd5），[Ir（η^6-pcp）（cod）]X（X= BF_46a; ClO_46b·CH_2Cl_2）和[Ir 2（η^6，η^6-pcp）（cod）_2]X_2 （X= BF_47a; ClO_47b），其中七种结构具有晶体特征。在复合体1·thf，2·CH_2Cl_2，3和6 b·CH_2Cl_2中，每一个Rh或Ir原子都是β ^6-连接到pep配体中的两个上层，以支持一个单核结构。average interannular distances between the two decks are 3.03（1·thf）、3.01 （2·CH_2 Cl_2）、3.04 （3）and 3.01（6 b·CH2Cl2）、respectively。在复合体4、5和7 b中，两个Rh或Ir原子是η^6-协调到胡椒配体中的上层和下层甲板，以提供一个核结构。两个甲板之间的平均间隔距离分别为3.04（4）、3.05（5）和3.05（5） ... More 3.05\（7 b）、respectively。关于复合体1·thf-7 b，在3.01至3.05之间发现的两个甲板的平均间隔距离比（3.09）的无金属胡椒配体短，建议两个甲板的再脉冲π-相互作用之间的金属片段与diene配体的协调减少。在添加中，内分子距离和两座乙基桥的配置之间的关系是显而易见的。如果间隔距离比3.05短，两个乙基桥的配置可能更有可能是扭曲的交叉类型，如果间隔距离比3.01短，则该配置可能更有可能是并行类型，用两个乙基桥的结构转换和两个甲板的滑动结合起来，新的两个indium terphenyl复合体也是准备好的及其结构were characterized crystallographically. CH_2Cl_2与p-terphenyl（p-tp）中的[Ir（cod）_2]BF_4与偶氮Ir（I）复合体{[Ir_2（p-tp）（cod）_2]（BF_4）_2·2CH_2Cl_2}_3的反应（8·2CH_2Cl_2），当中间人的反应发生的时候[编辑]（η 5-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）.在复合8·2CH_2Cl_2两个原子被η^6-协调从p-tp配体的上和下侧的终端苯环的两侧，当一个原子是η^6-协调到复合体中终端苯环的一面时，每个晶体结构都描述了金属复合体中的第一个协调模式，与m-和p-一起找到了金属复合体中的第一个协调模式。tp ligands。Less（低）

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