Synthesis and Molecular Structure of Gold Triarylcorroles

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• 作者：Kolle E. Thomas ; Abraham B. Alemayehu ; Jeanet Conradie ; Christine Beavers ; Abhik Ghosh
• 刊名：Inorganic Chemistry
• 出版年：2011
• 出版时间：December 19, 2011
• 年：2011
• 卷：50
• 期：24
• 页码：12844-12851
• 全文大小：474K
• 年卷期：v.50,no.24(December 19, 2011)
• ISSN：1520-510X

文摘

A 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 尾-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 鈥渋nherent saddling鈥?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鈥揷orrole 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)鈭抍orrole(鈥?鈭? to relatively innocent metal(III)鈭抍orrole(3鈭?.