Effect of second-sphere coordination. 10. Contribution of (pi)-electron acceptability of ancillary ligand to stability of 18-crown-6 ether adduct of ruthenium complex

The mono and dimetallic cyclometallated ruthenium complexes of dibenzo[a:c](dipyrido[2,3-h:2ʹ,3ʹ-j])phenazine (dbdpzH2) have been prepared. The monocyclometallation of this potentially dicyclometallating bridging ligand in the dimetallic complex: [(tpy)Ru (dbdpzH)Ru(H2O)(tpy)]3+ has been attributed to the distortion of the ligand upon binding to the first metal ion, which increases the size of the second binding site, inhibiting the second cyclometallation. The mono and dimetallic cyclometallated ruthenium complexes of dibenzo[a:c](dipyrido[2,3-h:2ʹ,3ʹ-j]) phenazine (dbdpzH2) have been prepared. The monocyclometallation of this potentially dicyclometallating bridging ligand in the dimetallic complex has been attributed to distortion of the second chelating site by the first complexation which inhibits the second cyclometallation.