Structure and Reactivity of One- and Two-Electron Oxidized Manganese(V) Nitrido Complexes Bearing a Bulky Corrole Ligand

Research output: Journal Publications and Reviews (RGC: 21, 22, 62)21_Publication in refereed journalpeer-review

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Author(s)

  • Runhui Liang
  • David Lee Phillips
  • Hung Kay Lee
  • Wai-Lun Man
  • Shek-Man Yiu
  • Tai-Chu Lau

Related Research Unit(s)

Detail(s)

Original languageEnglish
Pages (from-to)7588–7593
Journal / PublicationJournal of the American Chemical Society
Volume144
Issue number17
Publication statusAccepted/In press/Filed - 2022

Abstract

As a strategy to design stable but highly reactive metal nitrido species, we have synthesized a manganese(V) nitrido complex bearing a bulky corrole ligand, [MnV(N)(TTPPC)] (1, TTPPC is the trianion of 5,10,15-Tris(2,4,6-triphenylphenyl)- corrole). Complex 1 is readily oxidized by 1 equiv of Cp2Fe+ to give the neutral complex 2, which can be further oxidized by 1 equiv of [(p-Br-C6H4)3N•+ ][B(C6F5)4] to afford the cationic complex 3. All three complexes are stable in the solid state and in CH2Cl2 solution, and their molecular structures have been determined by X-ray crystallography. Spectroscopic and theoretical studies indicate that complexes 2 and 3 are best formulated as Mn(V) nitrido π-cation corrole [MnV(N)(TTPPC+• )] and Mn(V) nitrido π dication corrole [MnV(N)(TTPPC2+)]+ , respectively. Complex 3 is the most reactive N atom transfer reagent among isolated nitrido complexes; it reacts with PPh3 and styrene with second-order rate constants of 2.12 × 105 and 1.95 × 10−2 M−1 s −1 , respectively, which are >107 faster than that of 2.

Citation Format(s)

Structure and Reactivity of One- and Two-Electron Oxidized Manganese(V) Nitrido Complexes Bearing a Bulky Corrole Ligand. / Shi, Huatian; Liang, Runhui; Phillips, David Lee et al.

In: Journal of the American Chemical Society, Vol. 144, No. 17, 2022, p. 7588–7593.

Research output: Journal Publications and Reviews (RGC: 21, 22, 62)21_Publication in refereed journalpeer-review