Comparison of two MnIV MnIV -bis-μ-oxo complexes {[MnIV (N4 (6-Me-DPEN))]2 (μ-O)2 }2+ and {[MnIV (N4 (6-Me-DPPN))]2 (μ-O)2 }2

Acta Crystallographica. Section E, Crystallographic Communications
Michael K CogginsJulie A Kovacs

Abstract

The addition of tert-butyl hydro-peroxide ( t BuOOH) to two structurally related MnII complexes containing N,N-bis-(6-methyl-2-pyridyl-meth-yl)ethane-1,2-di-amine (6-Me-DPEN) and N,N-bis-(6-methyl-2-pyridyl-meth-yl)propane-1,2-di-amine (6-Me-DPPN) results in the formation of high-valent bis-oxo complexes, namely di-μ-oxido-bis-{[N,N-bis-(6-methyl-2-pyridylmeth-yl)ethane-1,2-di-amine]-manganese(II)}(Mn-Mn) bis-(tetra-phenyl-borate) dihydrate, [Mn(C16H22N4)2O2](C24H20B)2·2H2O or {[MnIV(N4(6-Me-DPEN))]2(μ-O)2}(2BPh4)(2H2O) (1) and di-μ-oxido-bis-{[N,N-bis-(6-methyl-2-pyridylmeth-yl)propane-1,3-di-amine]-manganese(II)}(Mn-Mn) bis-(tetra-phenyl-borate) diethyl ether disolvate, [Mn(C17H24N4)2O2](C24H20B)2·2C4H10O or {[MnIV(N4(6-MeDPPN))]2(μ-O)2}(2BPh4)(2Et2O) (2). Complexes 1 and 2 both contain the 'diamond core' motif found previously in a number of iron, copper, and manganese high-valent bis-oxo compounds. The flexibility in the propyl linker in the ligand scaffold of 2, as compared to that of the ethyl linker in 1, results in more elongated Mn-N bonds, as one would expect. The Mn-Mn distances and Mn-O bond lengths support an MnIV oxidation state assignment for the Mn ions in both 1 and 2. The angles around the Mn centers are con...Continue Reading

References

Jun 1, 1970·Photochemistry and Photobiology·B KokM McGloin
Dec 20, 2002·Angewandte Chemie·Lawrence Que, William B Tolman
Dec 25, 2007·Acta Crystallographica. Section A, Foundations of Crystallography·George M Sheldrick
Dec 17, 2008·Coordination Chemistry Reviews·Christopher S Mullins, Vincent L Pecoraro
Apr 2, 2011·Journal of Photochemistry and Photobiology. B, Biology·Gernot Renger
Jul 23, 2011·Journal of the American Chemical Society·Michael K Coggins, Julie A Kovacs
Apr 2, 2014·Chemical Reviews·Junko Yano, Vittal Yachandra
Jan 9, 2015·Acta Crystallographica. Section C, Structural Chemistry·George M Sheldrick
Sep 19, 2017·Journal of the American Chemical Society·Thomas LohmillerNicholas Cox
May 1, 2016·Chemical Physics Letters·Makoto HatakeyamaShinichiro Nakamura
Sep 5, 2019·Journal of the American Chemical Society·Penny Chaau Yan PoonJulie A Kovacs

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Citations

Apr 15, 2021·Journal of the American Chemical Society·Alexandra N DowningJulie A Kovacs

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