       Abstract
Heavy-element corroles are of great interest as optical sensors, near-IR dyes, phosphors, organic light-emitting diodes, and anticancer compounds. Insertion of 5d metals into corroles, however, is often a difficult and unpredictable process. Against this backdrop, oxidative metalation of meso triarylcorroles with [Os3(CO)12]/NaN3 in refluxing 1:2 diethylene glycol monomethyl ether/glycol has provided a convenient and relatively high-yielding route to nitridoosmium(VI) corroles, three of which could be characterized with single-crystal X-ray structure analysis.
Last man standing! After the synthesis of platinum corroles, osmium was the last remaining middle and late 5d metal to be inserted into the contracted porphyrin analogue. Oxidative metalation has now provided a moderately high-yielding route to osmium corroles. DEGME=diethylene glycol monomethyl ether.
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Electrochemical evidence that pyranopterin redox chemistry controls the catalysis of YedY, a mononuclear Mo enzyme
Hope Adamson a, Alexandr N. Simonov b, Michelina Kierzek c, Richard A. Rothery c, Joel H. Weiner c, Alan M. Bond b, and Alison Parkin a,1 a Department of Chemistry, University of York, Heslington, York YO10 5DD, United Kingdom; b School of Chemistry, Monash University, Clayton, VIC 3800, Australia; and c Department of Biochemistry, University of Alberta, Edmonton, AB T6G 2H7, Canada Edited by Harry B. Gray, California Institute of Technology, Pasadena, CA, and approved October 13, 2015 (received for review August 25, 2015) http://www.pnas.org/content/112/47/14506.short A long-standing contradiction in the field of mononuclear Mo enzyme research is that small-molecule chemistry on active-site mimic compounds predicts ligand participation in the electron transfer reactions, but biochemical measurements only suggest metal-centered catalytic electron transfer.With the simultaneous measurement of substrate turnover and reversible electron transfer that is provided by Fourier-...
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