ic202023r_si_001.pdf (156.49 kB)
Synthesis and Molecular Structure of Gold Triarylcorroles
journal contribution
posted on 2011-12-19, 00:00 authored by Kolle
E. Thomas, Abraham B. Alemayehu, Jeanet Conradie, Christine Beavers, Abhik GhoshA number of third-row transition-metal corroles have
remained elusive
as synthetic targets until now, notably osmium, platinum, and gold
corroles. Against this backdrop, we present a simple and general synthesis of β-unsubstituted gold(III) triarylcorroles and the first X-ray crystal structure
of such a complex. Comparison with analogous copper and silver corrole
structures, supplemented by extensive scalar-relativistic, dispersion-corrected
density functional theory calculations, suggests that “inherent
saddling” may occur for of all coinage metal corroles.
The degree of saddling, however, varies considerably among the three
metals, decreasing conspicuously along the series Cu > Ag >
Au. The
structural differences reflect significant differences in metal–corrole
bonding, which are also reflected in the electrochemistry and electronic
absorption spectra of the complexes. From Cu to Au, the electronic
structure changes from noninnocent metal(II)−corrole(•2−)
to relatively innocent metal(III)−corrole(3−).