Ring-size and substituent effects in relatively rigid macrocyclic quinquedentate ligands. Structure determinations of [ZnL<sup>4</sup>(H<sub>2</sub>O)<sub>2</sub>][ClO<sub>4</sub>]<sub>2</sub>·MeCN and [ZnL<sup>3</sup>(ClO<sub>4</sub>)<sub>2</sub>]
作者:David C. Liles、Mary McPartlin、Peter A. Tasker
DOI:10.1039/dt9870001631
日期:——
spectroscopic evidence show that the 15- and 16-membered ring ligands form seven-co-ordinate complexes in which the macrocycle defines the equatorial plane of an approximate pentagonal bipyramid and the axial sites are occupied by water molecules or co-ordinated anions. The geometry of the N3X2-donor set (X = O or S) and hence the goodness of fit for different metal ions depends crucially on the nature
从吡啶-2,6-二甲醛与α,ω-二苯胺之间的环缩合反应中分离出二十一个具有N 5-,N 3 O 2-和N 3 S 2-供体的大环五齿配体金属配合物[例如1 ,2-二(邻氨基苯硫基)乙烷]是在二价过渡金属盐的存在下进行的。X [ZNL的仪射线结构分析3(CLO 4)2 ]和[ZNL 4(H 2 O] [CLO 4 ] 2 ·的MeCN(L 3 =二氢-6,7- 15,19-nitrilodibenzo [e,p ] [1,4,7,15]-二硫杂氮杂环庚素,L 4 = 7,8-二氢-6 H -16,20-硝酰二苯并[ f,q ]-[1,5,8,16]二硫杂氮杂环-十八烷基)和光谱证据表明,15和16元环配体形成了7个坐标的配合物,其中大环定义了近似五边形双锥体的赤道面,轴向位点被水分子或共价键占据。阴离子。N 3 X 2供体组的几何形状(X = O或S)以及因此对不同金属离子的拟合优劣主要取决于大环中苯环之间桥的性质。