Although the affinity of metallocorroles to axial ligands is quite low,t his is not the case when the chelated element is phosphorus. This work is hence focusedo nt he mechanism of ligand exchange of six-coordinate phosphorus corroles as at ool for affecting their chemical and physical properties. These fundamental investigations allowed for the development of facile methodologies for the synthesis of a large series of complexes and the establishment of several new structure/activity profiles that may be used to understand and predict spectroscopic features and for tailor-made modification of photophysical and electrochemical properties. This is exemplified by the facile access to complexes with terminal groups that are of large potentialf or practical applicationsb ased on click chemistry,o ptical imaging, and surfacescience.Scheme1.Oxo-, hydroxo-and trans-bishydroxo-P V chelated by corrole, porphyrin, or phthalocyanine.[a] Q.

Rhodium insertion into the new 5,10,15,20-tetrakis(trifluoromethyl)sapphyrin was found to be much more facile than for other analogues, owing to NH⋅⋅⋅F hydrogen-bonding interactions that stabilise the pyrrole-inverted structure characteristic of the metallated product. The thus-obtained rhodium(I) complexes have axial chirality, and the enantiomers were resolved. The latter were found to interconvert quite rapidly in a process that involves a tautomerisation-like movement of the metal fragment between the five N atoms. The rhodium sapphyrins were investigated as catalysts for organic synthesis, by studying their carbene-transfer activity in the cyclopropanation of styrene with ethyl diazoacetate and comparing it to that of rhodium corroles.

Invited for the cover of this issue is the group of Zeev Gross at the Technion‐Israel Institute of Technology. The image, designed by Qiu‐Cheng Chen and Zeev Gross, was inspired by space walking and depicts rhodium(I) floating between the five nitrogen atoms of sapphyrin and how this affects chirality of the corresponding complex. Here the first co‐author, Q.‐C. Chen, shares some insights. Read the full text of the article at https://doi.org/10.1002/chem.201804138.

Rhodium(I) floating between the five nitrogen atoms of sapphyrin and how this affects chirality of the corresponding complex are depicted in the cover image. In addition, this work focuses on the CF3‐stabilized derivative and its ability to catalyze cyclopropanation. More information can be found in the Full Paper by Z. Gross et al. on page 17255.