Knaust Jacqueline M, Keller Steven W
Department of Chemistry, University of Missouri-Columbia, Columbia, MO 65203, USA.
Inorg Chem. 2002 Nov 4;41(22):5650-2. doi: 10.1021/ic025836c.
Reaction of [Cu(PPh(3))(2)(MeCN)(2)]PF(6) and trans-1,2-bis(4-pyridyl)ethylene (bpe) results in the trans-cis isomerization of the bpe and subsequent formation of a mixed-isomer linear coordination polymer over the course of several days or weeks depending on solvent. The one unique copper atom in the structure is coordinated to two bridging cis-bpe ligands, one bridging trans-bpe ligand, and one terminal triphenylphoshine ligand to create Cu(trans-bpe)(0.5)(cis-bpe)(PPh(3))( infinity ) zigzag chains. The reaction requires both visible light and Cu(I), and the crystallization of this particular coordination polymer is insensitive to the ratio of trans:cis isomers in solution, occurring both from trans-rich and cis-rich solutions.
[Cu(PPh(3))(2)(MeCN)(2)]PF(6) 与反式-1,2-双(4-吡啶基)乙烯 (bpe) 反应,会导致 bpe 发生反-顺异构化,并在数天或数周内根据溶剂情况随后形成混合异构体线性配位聚合物。结构中唯一的铜原子与两个桥连的顺式-bpe 配体、一个桥连的反式-bpe 配体和一个末端三苯基膦配体配位,形成 Cu(反式-bpe)(0.5)(顺式-bpe)(PPh(3))(∞) 之字形链。该反应需要可见光和 Cu(I),并且这种特定配位聚合物的结晶对溶液中反式:顺式异构体的比例不敏感,在富含反式和顺式的溶液中均会发生。