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 Brothers, Donald J. Darensbourg, Ashfaq A. Bengali

Research output: Contribution to journalArticle

28 Citations (Scopus)

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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Carbon Monoxide
Manganese
manganese
reactivity
Hot Temperature
Ligands
ligands
butadiene
dissolving
irradiation
room temperature
profiles
Light
interactions
Dissolution
Irradiation
Temperature

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry
  • Inorganic Chemistry

Cite this

Thermal and photochemical reactivity of manganese tricarbonyl and tetracarbonyl complexes with a bulky diazabutadiene ligand. / Yempally, Veeranna; Kyran, Samuel J.; Raju, Rajesh K.; Fan, Wai Yip; Brothers, Edward; Darensbourg, Donald J.; Bengali, Ashfaq A.

In: Inorganic Chemistry, Vol. 53, No. 8, 21.04.2014, p. 4081-4088.

Research output: Contribution to journalArticle

Yempally, Veeranna ; Kyran, Samuel J. ; Raju, Rajesh K. ; Fan, Wai Yip ; Brothers, Edward ; Darensbourg, Donald J. ; Bengali, Ashfaq A. / Thermal and photochemical reactivity of manganese tricarbonyl and tetracarbonyl complexes with a bulky diazabutadiene ligand. In: Inorganic Chemistry. 2014 ; Vol. 53, No. 8. pp. 4081-4088.
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AU - Brothers, Edward

AU - Darensbourg, Donald J.

AU - Bengali, Ashfaq A.

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AB - 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.

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