The synthetic macrocyclic ligand rac-5,7,7,12,12,14-hexamethy 1-1,4,8,11 -tetraazacyclotetradecane (rac-5,14-aneN4) has been resolved via its nickel(ll) complex. The optically active ligand has been removed from Ni(II) and transferred to copper(II) and manganese(III). A circular dichroism analysis of (+)[Mn((–)5,14-aneN4)X2]PF6, where X- is Cl- or Br-, has been very useful in interpreting the electronic spectrum of this tetragonally distorted high-spin d4 system. The macrocyclic crystal field (10Dq) for Mn(III) as measured by the position of the 5B1g → 5B2g electronic transition was found to be about 23 kK.
ASJC Scopus subject areas
- Physical and Theoretical Chemistry
- Inorganic Chemistry