2005
DOI: 10.1021/ic0484506
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High-Valent Imido Complexes of Manganese and Chromium Corroles

Abstract: 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 An… Show more

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Cited by 83 publications
(58 citation statements)
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“…6 As part of our interest in developing nitrene (NR) transfer to organic substrates by transition‐metal catalysis, we have used aryl azides, which are quite stable and easy to make,7, 8 to prepare mononuclear terminal imido complexes of manganese( V ) and chromium( V ) corroles 9. 10 Despite many known reactions of organic azides with transition metals, little is known about the reaction mechanism. Organoazido metal complexes have been proposed to initially form for coordinatively unsaturated metal complexes 11–14.…”
Section: Methodsmentioning
confidence: 99%
See 1 more Smart Citation
“…6 As part of our interest in developing nitrene (NR) transfer to organic substrates by transition‐metal catalysis, we have used aryl azides, which are quite stable and easy to make,7, 8 to prepare mononuclear terminal imido complexes of manganese( V ) and chromium( V ) corroles 9. 10 Despite many known reactions of organic azides with transition metals, little is known about the reaction mechanism. Organoazido metal complexes have been proposed to initially form for coordinatively unsaturated metal complexes 11–14.…”
Section: Methodsmentioning
confidence: 99%
“…All other solvents and reagents were of reagent grade and used as received. The syntheses of H 3 (tpfc),28, 29 [Mn(tpfc)],30 [Cr(tpfc)(py 2 )],31 [Mn(tpfc)(NMes)]9 (Mes=2,4,6‐(CH 3 ) 3 C 6 H 2 ), [Mn(tpfc)(NAr)]9 (Ar=2,4,6‐Cl 3 C 6 H 2 ), [Mn(tpfc)(NAr′)]10 (Ar′=2,6‐Cl 2 C 6 H 3 ), [Cr(tpfc)(NMes)],10 and [Cr(tpfc)(NAr)]10 followed previously described methods. All azides were prepared by using the Sandmeyer reaction or slight variations thereof 7.…”
Section: Methodsmentioning
confidence: 99%
“…[7,8] Moreover, compound 1 was more planar than its corresponding free-base corrole [14] and metallocorroles. [15] In the free-base corrole, the three inner NH protons caused steric crowding, thereby resulting in strain in the corrole macrocycle. On complexation with small P V ions, the strain imposed by the inner NH protons was released and the corrole ring became more planar in compound 1.…”
Section: Crystallographic Characterization: Further Confirmation Of Tmentioning
confidence: 99%
“…For the internal tautomer, removal of the three protons will result in a trianionic macrocycle that could stabilize high valent states in metal ions. This would be similar to the high valent stabilizations seen in corrole and triazacorrole metal complexes [28,29]. One distinct advantage of N-confused porphyrin is that it has the same steric footprint as normal porphyrin, and thus the same metal binding pore size.…”
Section: N-confused Porphyrin As a Ligandmentioning
confidence: 54%