[40]nonaphyrin(1.1.1.1.1.1.1.1.1) and its heterometallic complexes with palladium-carbon bonds.
meso-Pentafluorophenyl- substituted [40]nonaphyrin(1.1.1.1.1.1.1.1.1) 3 has been prepared by using a stepwise ring-size-selective synthesis, and has been reduced with NaBH(4) to [42]nonaphyrin(1.1.1.1.1.1.1.1.1) 5. Structurally, 3 is characterized by a figure-of-eight shape, consisting of a porphyrin-like tetrapyrrolic segment and a hexaphyrin-like hexapyrrolic segment, whereas 5 has been found to adopt a distorted nonplanar butterfly-like shape. In the mono-metal complexes 6 and 7, a Zn(II) or Cu(II) ion is bound by the porphyrin-like tetrapyrrolic segment, maintaining the overall structure of 3. Similarly to 3, complexes 6 and 7 are interconvertible with the corresponding complexes 9 and 10 through two-electron reduction with NaBH(4) and oxidation with DDQ. The metal-free hexaphyrin-like segments of 6 and 7 have been shown to serve as a suitable platform for the complexation of two palladium ions, providing hetero-trinuclear metal complexes 11 (Zn(II)-Pd(II)-Pd(II)) and 13 (Cu(II)-Pd(II)-Pd(II)) in high yields, in which the Zn or Cu ion resides at the same porphyrin-like segment, and one Pd ion is bound in an NNCC fashion through double C--H bond activation while the other is bound in an NNC fashion with single C--H bond activation. Multi-metal complexes 11, 12, and 13 exhibit small electrochemical HOMO-LUMO gaps (<0.6 eV), despite their nonplanar conformations.
Kamimura
Yiho
Y
Department of Chemistry, Graduate School of Science, Kyoto University, and Core Research for Evolutional Science and Technology (CREST), Japan.
Shimizu
Soji
S
Osuka
Atsuhiro
A