Itai Takuma, Kojima Tatsuhiro, Kuwamura Naoto, Konno Takumi
Department of Chemistry, Graduate School of Science, Osaka University, Toyonaka, Osaka, 560-0043, Japan.
Chemistry. 2017 Nov 21;23(65):16438-16441. doi: 10.1002/chem.201703350. Epub 2017 Aug 23.
A unique example of a coordination system that creates optically pure crystals from a meso compound with d- and l-amino acids is reported. The 1:1 reaction of a newly prepared meso digold(I) complex, [Au (dcpe)(d-Hpen)(l-Hpen)] ([H 1]), with Co(OAc) under aerobic conditions yielded a cationic Au Co trinuclear complex, [Au Co(dcpe)(d-pen)(l-pen)] [2] , in which [1] acts as a hexadentate-N ,O ,S metalloligand to a Co center. Similar reactions with M(OAc) (M=Ni and Zn) produced analogous but neutral Au M complexes, [Au M(dcpe)(d-pen)(l-pen)] ([3 ]). Complexes [2] and [3 ] are chiral (C vs. A) at the octahedral Co and M centers due to the arrangement of the N ,O ,S donor set. In addition, through spontaneous resolution, [3 ] gave optically pure C-[3 ] and A-[3 ] crystals, showing the creation of homochirality from meso-[1] and achiral M through crystallization. Such a phenomenon was not observed for [2] , which gave a racemic compound containing both C-[2] and A-[2] .
报道了一种独特的配位体系实例，该体系能从含有d-和l-氨基酸的内消旋化合物中生成光学纯晶体。新制备的内消旋二金（I）配合物[Au (dcpe)(d-Hpen)(l-Hpen)]（[H 1]）与Co(OAc)在有氧条件下以1:1反应，生成阳离子型金钴三核配合物[Au Co(dcpe)(d-pen)(l-pen)] [2]，其中[1]作为六齿-N、O、S金属配体与Co中心配位。与M(OAc)（M = Ni和Zn）的类似反应生成了类似但呈中性的金M配合物[Au M(dcpe)(d-pen)(l-pen)]（[3 ]）。由于N、O、S供体基团的排列，配合物[2]和[3 ]在八面体Co和M中心处具有手性（C型对A型）。此外，通过自发拆分，[3 ]生成了光学纯的C-[3 ]和A-[3 ]晶体，表明通过结晶从内消旋-[1]和非手性M产生了同手性。对于[2]未观察到这种现象，[2]生成了同时含有C-[2]和A-[2]的外消旋化合物。
