Thermal and photochemical reactivity of manganese tricarbonyl and tetracarbonyl complexes with a bulky diazabutadiene ligand

Veeranna Yempally, Samuel J. Kyran, Rajesh K. Raju, Wai Yip Fan, Edward N. Brothers, Donald J. Darensbourg, Ashfaq A. Bengali

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Abstract

The manganese tricarbonyl complex fac-Mn(Br)(CO)3( iPr2Ph-DAB) (1) [iPr2Ph-DAB = (N,N′-bis(2,6-di-isopropylphenyl)-1,4-diaza-1,3-butadiene)] was synthesized from the reaction of Mn(CO)5Br with the sterically encumbered DAB ligand. Compound 1 exhibits rapid CO release under low power visible light irradiation (560 nm) suggesting its possible use as a photoCORM. The reaction of compound 1 with TlPF6 in the dark afforded the manganese(I) tetracarbonyl complex, [Mn(CO)4(iPr 2Ph-DAB)][PF6] (2). While 2 is comparatively more stable than 1 in light, it demonstrates high thermal reactivity such that dissolution in CH3CN or THF at room temperature results in rapid CO loss and formation of the respective solvate complexes. This unusual reactivity is due to the large steric profile of the DAB ligand which results in a weak Mn-CO binding interaction.

Original languageEnglish
Pages (from-to)4081-4088
Number of pages8
JournalInorganic Chemistry
Volume53
Issue number8
DOIs
Publication statusPublished - 21 Apr 2014

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ASJC Scopus subject areas

  • Physical and Theoretical Chemistry
  • Inorganic Chemistry

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