No abstract

Endlich, die terminalen Mangan(v)‐Imidokomplexe, die postulierten Zwischenprodukte von Aminierungs‐ und Aziridinierungsreaktionen, wurden hergestellt. Die Synthese der strukturell gut charakterisierten (Imido)mangan(v)‐Corrole 2 und 3, die mit elektronenreichen Nucleophilen wie organischen Phosphanen reagieren, beruht auf der Reaktion von Mangan(III)‐Corrolen mit organischen Aziden unter Photolysebedingungen.

At last, terminal imido complexes of manganese(V), the postulated intermediates in aziridination and amination reactions, have been prepared. The structurally well‐defined (imido)manganese(V) corroles, 2 and 3, are easily synthesized from manganese(III) corroles with organic azides under photolysis conditions and react with electron‐rich nucleophiles such as organic phosphanes.

The oxidation reaction of M(tpfc) [M = Mn or Cr and tpfc = tris(pentafluorophenyl)corrole] with aryl azides under photolytic or thermal conditions gives the first examples of mononuclear imido complexes of manganese(V) and chromium(V). These complexes have been characterized by NMR, mass spectrometry, UV-vis, EPR, elemental analysis, and cyclic voltammetry. Two X-ray structures have been obtained for Mn(tpfc)(NMes) and Cr(tpfc)(NMes) [Mes = 2,4,6-(CH(3))(3)C(6)H(2)]. Short metal-imido bonds (1.610 and 1.635 Angstroms) as well as nearly linear M-N-C angles are consistent with triple M triple-bond NR bond formation. The kinetics of nitrene [NR] group transfer from manganese(V) corroles to various organic phosphines have been defined. Reduction of the manganese(V) corrolato complex affords phosphine imine and Mn(III) with reaction rates that are sensitive to steric and electronic elements of the phosphine substrate. An analogous manganese complex with a variant corrole ligand containing bromine atoms in the beta-pyrrole positions, Mn(Br(8)tpfc)(NAr), has been prepared and studied. Its reaction with PEt(3) is 250x faster than that of the parent tpfc complex, and its Mn(V/IV) couple is shifted by 370 mV to a more positive potential. The EPR spectra of chromium(V) imido corroles reveal a rich signal at ambient temperature consistent with Cr(V) triple-bond NR (d(1), S = 1/2) containing a localized spin density in the d(xy) orbital, and an anisotropic signal at liquid nitrogen temperature. Our results demonstrate the synthetic utility of organic aryl azides in the preparation of mononuclear metal imido complexes previously considered elusive, and suggest strong sigma-donation as the underlying factor in stabilizing high-valent metals by corrole ligands.