Oxidative Metalation as a Route to Size‐Mismatched Macrocyclic Complexes: Osmium Corroles

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.

Ligand Noninnocence in Coinage Metal Corroles: A Silver Knife‐Edge

“…For class Im etallocorroles, which include Cu, [21] FeCl, [17] FeNO, [29] and MnCl [19] corroles among others, the Soret maximum redshifts markedly in response to increasingly electron-donating character of the substituent X. For class II metallocorroles, which include Au, [11a,b] CrO, [24] MoO, [24] and OsN [25] corrolesa mong others, the Soret maximum exhibitsn os uch sensitivity to X. Over the course of severals tudies, it has become clear that class Im etallocorroles have noninnocent corrole ligandsw ith significant to full-fledged corroleC 2À character.T he substituent sensitivity of the Soret maximumi st hen thought to arise from one or more transitions with aryl-to-corrole charge-transfer character in the Soret region.…”

Relativistic effects in metallocorroles: comparison of molybdenum and tungsten biscorroles

“…Important opportunities in this regard are provided by recent syntheses of several 5d metallocorroles, 11,12,13,14,15,16,17,18 which have garnered attention as unique size-mismatched complexes combining a large 5d transition metal and a sterically constrained corrole ligand. Thus, in a recent study, we were able to attribute a ~28-nm redshift in the Soret maxima of rhenium(V)-oxo corroles, relative to analogous technetium(V)-oxo corroles, to relativistic effects.…”

Metal–Ligand Misfits: Facile Access to Rhenium–Oxo Corroles by Oxidative Metalation

“…[1] Recent efforts by ah andful of groups,i ncluding ours, have led to the synthesis of several such complexes,i ncluding Hf, [2] W, [3] Os, [4] Ir, [5] Pt, [6] and Au [7] corroles. Unsurprisingly,s ome of the syntheses are difficult and low-yielding.…”

“…[6] By contrast, Ir andO s corrolesa re comparatively easily obtained and also in reasonably good yields. [4,5] There are good reasons for seeking improveds ynthetic routes to the 5d metallocorroles. For example, gold corrolesh ave found applicationsi no rganic solar cells and the photodynamic therapy of cancer.…”

“…[11] Furthermore, an efficient route to rheniumc orroles may pave the way to an analogousr oute to technetium corroles. [12] We were delighted to discover that an oxidative metalation protocol, akin to the one used for Os corroles, [4] 10 ]i nr efluxing decalin in af ew hours and in yields of 62-84 %(Scheme 1).…”