Structure of the copper(II) complex of the reinforced ligand N,N'-bis(trans-2-hydroxycyclohexyl)-trans-cyclohexane-1,2-diamine and the metal-ion-size-based selectivity produced by cyclohexanediyl bridges

被引:19
作者
DeSousa, AS
Hancock, RD
Reibenspies, JH
机构
[1] UNIV WITWATERSRAND,DEPT CHEM,JOHANNESBURG,SOUTH AFRICA
[2] TEXAS A&M UNIV,DEPT CHEM,COLLEGE STN,TX 77843
来源
JOURNAL OF THE CHEMICAL SOCIETY-DALTON TRANSACTIONS | 1997年 / 16期
关键词
D O I
10.1039/a700759k
中图分类号
O61 [无机化学];
学科分类号
070301 ; 081704 ;
摘要
The compound N,N'-bis(2-hydroxycyclohexyl)-trans-cyclohexane-1,2-diamine (L-1) and its complex with Cu-II have been prepared. The structure of [CuL1][ClO4](2) 1 was determined. The Cu has a distorted octahedral coordination, with the four donor atoms provided by L-1 giving Cu-N 1.985(7) and Cu-O 1.947(6) Angstrom. The oxygens from two perchlorates lie on the axial positions with Cu-O 2.749 Angstrom. The perchlorates are involved in a hydrogen bonding network holding layers of [CuL1](2+) cations together with bonds to the hydrogens of the co-ordinated hydroxyls of the cyclohexanediyl groups and the NH hydrogens. Alternating layers of [CuL1](2+) cations have the L-1 ligand as the SRS and RSR enantiomers. Difficulty in obtaining a sufficiently large data set for L-1 meant that R for this structure was not less than 0.13. The structure is thus not reported in any detail, but is sufficient to indicate the conformation of the ligand, which is used as the basis of a molecular mechanics generation of the structure. Both the copper(II) complex of L-1 and L-1 itself have only the RSR and SRS diastereomeric pair present in the structures, supporting the idea that syntheses involving reaction of cyclohexene oxide with polyamines result in considerable diastereoselectivity. The structure of 1 shows steric crowding, with van der Waals repulsion between hydrogens on adjacent cyclohexyl groups of the L-1 ligand. This crowding becomes more severe as the metal ion becomes larger, which is related to the strong preference the ligand shows for smaller metal ions. This latter effect is indicated by the formation constants (log K-1) of L-1: Cu-II, 11.50; Ni-II, 6.84; Zn-II, 4.77; Cd-II, 4.08; Pb-II, 4.80; in 0.1 mol dm(-3) NaNO3 at 25 degrees C. The effect of cyclohexanediyl bridges on the stability of complexes formed by L-1 is discussed in relation to the stability of complexes of similar ligands that have simple ethylene bridges between their donor atoms.
引用
收藏
页码:2831 / 2835
页数:5
相关论文
共 20 条