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

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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