Generation of a Mn(IV)–Peroxo or Mn(III)–Oxo–Mn(III)
Species upon Oxygenation of Mono- and Binuclear Thiolate-Ligated Mn(II)
Complexes
Posted on 2017-08-21 - 18:59
A thiolate-bridged
binuclear complex [PPN]2[(MnII(TMSPS3))2] (1, PPN = bis(triphenylphosphine)iminium
and TMSPS3H3 = (2,2′,2″-trimercapto-3,3′,3″-tris(trimethylsilyl)triphenylphosphine)),
prepared from the reaction of MnCl2/[PPN]Cl and Li3[TMSPS3], converts into a mononuclear complex [PPN][MnII(TMSPS3)(DABCO)] (2) in the presence
of excess amounts of DABCO (DABCO = 1,4-diazabicyclo[2.2.2]octane).
Variable temperature studies of solution containing 1 and DABCO by UV–vis spectroscopy indicate that 1 and 2 exist in significant amounts in equilibrium and
mononuclear 2 is favored at low temperature. Treatment
of 1 or 2 with the monomeric O2-side-on-bound [PPN][MnIV(O2)(TMSPS3)] (3) produces the mono-oxo-bridged dimer [PPN]2[(MnIII(TMSPS3))2(μ-O)]
(4). The electrochemistry of 1 and 2 reveals anodic peak(s) for a MnIII/MnII redox couple at shifted potentials against Fc/Fc+, indicating
that both complexes can be oxidized by dioxygen. The O2 activation mediated by 1 and 2 is investigated
in both solution and the solid state. Microcrystals of 2 rapidly react with air or dry O2 to generate the Mn(IV)–peroxo 3 in high yield, revealing a solid-to-solid transformation
and two-electron reduction of O2. Oxygenation of 1 or 2 in solution, however, is affected by diffusion
and transient concentration of dioxygen in the two different substrates,
leading to generation of 3 and 4 in variable
ratios.
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Lee, Chien-Ming; Wu, Wun-Yan; Chiang, Ming-Hsi; Bohle, D. Scott; Lee, Gene-Hsiang (2017). Generation of a Mn(IV)–Peroxo or Mn(III)–Oxo–Mn(III)
Species upon Oxygenation of Mono- and Binuclear Thiolate-Ligated Mn(II)
Complexes. ACS Publications. Collection. https://doi.org/10.1021/acs.inorgchem.7b01513
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AUTHORS (5)
CL
Chien-Ming Lee
WW
Wun-Yan Wu
MC
Ming-Hsi Chiang
DB
D. Scott Bohle
GL
Gene-Hsiang Lee