Nishiura Misa, Kojima Tatsuhiro, Igashira-Kamiyama Asako, Konno Takumi
Department of Chemistry, Graduate School of Science, Osaka University, Toyonaka, Osaka, 560-0043, Japan.
Faculty of Law, Meiji Gakuin University, Totsuka-ku, Yokohama, Kanagawa, 244-8539, Japan.
Chem Asian J. 2018 May 28. doi: 10.1002/asia.201800835.
A unique example of a ring-to-cage structural conversion in a multinuclear gold(I) coordination system with d-penicillamine (d-H pen) is reported. The reaction of [Au Cl (dppe)] (dppe=1,2-bis(diphenylphosphino)ethane) with d-H pen in a 1:1 ratio gave [Au (dppe) (d-pen) ] ([1]), in which two [Au (dppe)] units are linked by two d-pen S atoms in a cyclic form so as to have two bidentate-N,O coordination arms. The subsequent reaction of [1] with Cu(OTf) afforded [Au Cu(dppe) (d-pen) ] ([2] ), in which a Cu ion is chelated by the two coordination arms in [1] to form an Au Cu bicyclic metallocage. A similar reaction using Cu(NO ) was accompanied by the ring expansion of [1] to [Au (dppe) (d-pen) ], leading to the production of [Au Cu (dppe) (d-pen) ] ([3] ). In [3] , two Cu ions are each chelated by the two coordination arms to form an Au Cu tricyclic metallocage, accommodating a nitrate ion. The use of Ni(NO ) or Ni(OAc) instead of Cu(NO ) commonly gave a tricyclic metallocage of [Au Ni (dppe) (d-pen) ] ([4] ), but a water molecule was accommodated inside the Au Ni metallocage.
报道了在多核金（I）与d-青霉胺（d-H pen）的配位体系中，从环状结构到笼状结构转变的一个独特例子。[Au Cl (dppe)]（dppe = 1,2-双（二苯基膦基）乙烷）与d-H pen以1:1的比例反应得到[Au (dppe) (d-pen) ]（[1]），其中两个[Au (dppe)]单元通过两个d-pen的S原子以环状形式相连，从而具有两个双齿-N,O配位臂。随后[1]与Cu(OTf)反应得到[Au Cu(dppe) (d-pen) ]（[2]），其中一个Cu离子被[1]中的两个配位臂螯合，形成一个Au Cu双环金属笼。使用Cu(NO₃)₂进行类似反应时，[1]会发生环扩展生成[Au₂(dppe) (d-pen)₂]，进而生成[Au₂Cu₂(dppe) (d-pen)₂]（[3]）。在[3]中，两个Cu离子分别被两个配位臂螯合，形成一个容纳硝酸根离子的Au₂Cu₂三环金属笼。使用Ni(NO₃)₂或Ni(OAc)₂代替Cu(NO₃)₂通常会得到[Au₂Ni₂(dppe) (d-pen)₂]（[4]）的三环金属笼，但在Au₂Ni金属笼内部容纳了一个水分子。
