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

Huatian Shi, Runhui Liang, David Lee Phillips, Hung Kay Lee, Wai Lun Man, Kai Chung Lau, Shek Man Yiu, Tai Chu Lau*

*Corresponding author for this work

Research output: Contribution to journalArticlepeer-review

1 Citation (Scopus)

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 CH2Cl2solution, 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 PPh3and styrene with second-order rate constants of 2.12 × 105and 1.95 × 10-2M-1s-1, respectively, which are >107faster than that of 2.

Original languageEnglish
Pages (from-to)7588-7593
Number of pages6
JournalJournal of the American Chemical Society
Volume144
Issue number17
Early online date20 Apr 2022
DOIs
Publication statusPublished - 4 May 2022

Scopus Subject Areas

  • Catalysis
  • Chemistry(all)
  • Biochemistry
  • Colloid and Surface Chemistry

Fingerprint

Dive into the research topics of 'Structure and Reactivity of One- and Two-Electron Oxidized Manganese(V) Nitrido Complexes Bearing a Bulky Corrole Ligand'. Together they form a unique fingerprint.

Cite this