Inorg. Chem. 1986, support the electron-transfer scheme shown in Figure 5. In the presence of 0.1 M C1-, the first reduction involves (P)InCl and [(P)InCl]-while the second reduction involves both [(P)InCl]-and (P)In(py)z, which is formed after C1-dissociation. This is illustrated by the voltammogram at 0.1 V/s. At 15 V/s, dissociation of CI-does not occur during the time scale of the measurement and only the top set of electrode reactions in Figure 5 take place. At all other scan rates, intermediate behavior is observed, and between two and four oxidation peaks are obtained depending upon scan rate.In conclusion, the electrochemical studies are consistent with the ligand-addition reactions reported earlier for the (P)InX system.l0 The formation of a mono-and bis(N-methylimidazole) adduct is observed by electrochemistry for all of the neutral compounds but the formation of bis(pyridine) adducts is observed only for the S03R-derivatives. The electrochemistry also provides information on nitrogenous base addition to the species formed 25, 26 17-2622 2617 after reduction by one or two electrons. In the presence of pyridine or N-MeIm the formation of [(P)InX(L)]-or (P)In(L)z is observed after reduction by one electron. The exact species formed is dependent upon both the nature of the axial ligand and the ligand concentration. However, after the addition of a second electron to [(P)InX(L)]-or (P)In(L)z, a pentacoordinated indium porphyrin dianion is always formed. Acknowledgment. The support of the National Science Foundation (Grant CHE-82 15507) is gratefully acknowledged. Registry No. N-MeIm, 616-47-7; (TPP)InS03Ph, 70619-92-0; (TP-P)InS03CH3, 70619-88-4; (TPP)InCI, 63128-70-1; (TPP)InOAc, 96150-61-7; (OEP)InSO,Ph, 70619-98-6; (OEP)InS03CH3, 70619-94-2;(OEP)InCI, 32125-07-8; (OEP)InOAC, 961 50-60-6; (TPP)InS03Ph(NThe circularly polarized luminescence (CPL) and total luminescence (TL) spectra are reported for aqueous solutions of tris complexes of Tb(III), Eu(III), Sm(III), and Dy(II1) with 2,6-pyridinedicarboxylic acid in basic media. The optical activity is generated from these racemic solutions by using as the excitation source circularly polarized Ar ion laser lines. No CPL was observed from similarly prepared solutions of Tb(III), Eu(III), and Sm(1II) with oxydiacetic acid. CPL was measured for the aqueous complex of Dy(II1) with oxydiacetic acid. These results are interpreted in terms of the kinetic stability of the complexes formed, and comparisons are made with other optical and with NMR measurements.
