Bulletin of Japan Society of Coordination Chemistry
Online ISSN : 1883-1737
Print ISSN : 1882-6954
ISSN-L : 1882-6954
Volume 60
Displaying 1-4 of 4 articles from this issue
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  • Hiroaki Ozawa, Masa-aki Haga
    2012 Volume 60 Pages 2-23
    Published: November 30, 2012
    Released on J-STAGE: March 12, 2013
    JOURNAL FREE ACCESS
    Assembling functional coordination compounds into nano-scaled architectures on solid surfaces is a fundamental topic of nanomaterial science because of tremendous applications in electronics and biological devices. This review focuses on the use of self-assembled monolayer(SAM) as a platform for the functionalization of solid surfaces such as ITO and nanocarbons(graphene and nanotube). The recent advances for self-assembling of organic phosphonic acids on metal oxide have been surveyed, and then the immobilization of redox-active Ru/Os complexes bearing multipod phosphonic acids onto ITO has been discussed from the viewpoint of molecular orientation and the merit of multipod anchoring on surface. Following self-assembly of the primer layer on solid surface, layer-by-layer growth of the molecular units by coordination programming has been discussed. Characterization of surface-confined SAM films based on redox-active complexes has been discussed about how to characterize nano-scaled films on solid surface. Chemical functions of multilayer films directed toward molecular electronics have been reviewed with respect to molecular memory, single molecular conductance, and molecular wires. However, there are a lot of challenging issues left to be tackled such as the surface metal-organic frameworks, photo responsive devices, and molecular sensing surface mimicking human five senses.
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Review
  • Wei-Yi Wu, Ken Kamikawa
    2012 Volume 60 Pages 24-31
    Published: November 30, 2012
    Released on J-STAGE: March 12, 2013
    JOURNAL FREE ACCESS
    In this review, haptotropic isomerizations and arene ligand exchange reactions of the tircarbonyl chromium complexes have been reported. Haptotropic metal migration reactions are well known phenomena for theπ-arene chromium complexes possessing the fused arene rings. Proper adjustment of the template allows for a photo induced reverse migration of the metal moiety, which can be utilized for the switchable organometallic device. Not only for the naphthalene chromium complex but also tri, tetra and pentacyclic fused system can be utilized for the reactions. Arene exchange reaction in arene chromium complex is also well known reaction. Basically, arene exchange reactions require high temperature (140-180 °C) in the presence of a large excess of the incoming arene. However, a couple of efforts to accelerate the ligand exchange have been developed. Basic concept for the acceleration is the design of a ligand to promote the formation of η4-intermediate which is one of late determined steps in this reaction. In recent years, chromium tricarbonyl group migration reaction can be utilized as a mobile chiral auxiliary for the stereoselective migration reactions.
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Topics
  • Shohei Tashiro
    2012 Volume 60 Pages 32-34
    Published: November 30, 2012
    Released on J-STAGE: March 12, 2013
    JOURNAL FREE ACCESS
    Porous metal complexes such as metal-organic framework (MOF) and porous coordination polymer (PCP) are one of the current attractive structural motifs because of their utility for several practical applications such as storage and separation of ions/molecules, catalysis, and proton conduction. Herein, this paper focuses on coordinatively unsaturated sites arranged in porous metal complexes as useful function centers. For example, unsaturated sites of Cu(II) and Zn(II) in two porous metal complexes, Cu3(btc)2 (btc = 1,3,5-benzenetricarboxylate) and Zn2(dobdc) (dobdc = 2,5-dioxido-1,4-benzenedicarboxylate), respectively, serves as good binding sites for hydrogen molecules as proven by neutron powder diffraction. Similar ferrous MOF, Fe2(dobdc), also realized the separation of olefin and paraffin gases through strong interaction between olefin molecules and the unsaturated Fe(II) sites. Furthermore, it was found that the unsaturated sites of Fe2(dobdc) could bind oxygen molecules through redox reaction to generate Fe(II/III)-O2- or Fe(III)-O22- species depending on the temperature. Therefore, application of the unsaturated coordination sites of MOF/PCP is promising not only for gas storage, separation and catalysis but also for a field of bioinorganic chemistry as active site models of metalloenzymes.
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Topics
  • Makoto Tanabe
    2012 Volume 60 Pages 34-37
    Published: November 30, 2012
    Released on J-STAGE: March 12, 2013
    JOURNAL FREE ACCESS
    The catalytic dehydrocoupling reactions of amine-boranes have attracted considerable interest from the perspectives of chemical hydrogen storage and the production of new inorganic polymers. In this review, significant progress made in coordination of amine-boranes at transition metals is described, and the elementary reactions in relation to the catalyzed dehydrocoupling process are also discussed. Highly unsaturated complexes as the precursors provide an efficient strategy to synthesize the complexes with amine-borane ligands. The amine-borane s-complexes with the h1- or h2-coordination modes consist of electron-donation from the B-H bond to the metals exclusively and negligible back-donation to the B-H bond. The B-H activation (oxidative addition) of amine-boranes is achieved to the unsaturated Rh-PR3 system, giving unique dimeric complexes with Me3N-stabilized boryl ligands. The iridium amine-borane s-complexes convert thermally to the complexes with amino-borane ligands, together with elimination of hydrogen. X-ray crystallographic results of the ruthenium amino-borane s-complexes display shortening of the Ru-B and B-N bonds, indicating the B-N multiple-bond character. Dehydrocoupling reactions of primary and secondary amine-boranes promoted by a cationic iridium complex produce the linear diborazanes as kinetically stable products. The reaction pathway of the dehydrogenative oligomerization of amino-boranes is proposed.
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