Synthesis and Structure of Ruthenocene-conjugated Microcyclic Triaza Crown Ether

Protonated N-(ruthenocenylmethyl)-1,4,7-triazacyclononane(1) and N, N′, N″-tris-(ruthenocenylmethyl)-1, 4, 7-triazacyclononane (2) were prepared and characterized. The structure of 2 was determined by X-ray crystallographic method. The crystal belongs to P21/a space group and cell parameters are a=1.428 5(3) nm, b=1.988 8(3) nm, c= 1. 913 3(3) nm; β=109.12(2)°; V=5.135 8(1.0) nm3; Z=4. Dc=1.665 g/cm3.1H NMR spectra of 1 and 2 revealed that the absorptions of the protons on substituted Cp rings in these compounds had a down-field shift from those of the protons on the Cp rings of ruthenocene. The observation suggests that the protonated 1,4, 7-triazacyclononane has a deshielding effect on the protons of the ruthenocene units. The CV curve of 2 gave an oxidation wave at 0. 84 V.