期刊
CHEMISTRY-A EUROPEAN JOURNAL
卷 20, 期 45, 页码 14584-14588出版社
WILEY-V C H VERLAG GMBH
DOI: 10.1002/chem.201404349
关键词
manganese; oxygen-atom-transfer; porphyrinoids; spin state reactivity; sulfoxidation
资金
- NSF [CHE0909587, CHE121386]
- NIH [GM101153]
- BBSRC
- EPSRC [EP/J003921/1] Funding Source: UKRI
- Engineering and Physical Sciences Research Council [EP/J003921/1] Funding Source: researchfish
Addition of an anionic donor to an Mn-V(O) porphyrinoid complex causes a dramatic increase in 2-electron oxygen-atom-transfer (OAT) chemistry. The 6-coordinate [Mn-V(O)(TBP(8)Cz)(CN)](-) was generated from addition of Bu4N+CN- to the 5-coordinate Mn-V(O) precursor. The cyanide-ligated complex was characterized for the first time by Mn K-edge X-ray absorption spectroscopy (XAS) and gives MnO=1.53 angstrom, MnCN=2.21 angstrom. In combination with computational studies these distances were shown to correlate with a singlet ground state. Reaction of the CN- complex with thioethers results in OAT to give the corresponding sulfoxide and a 2e(-)-reduced Mn-III(CN)(-) complex. Kinetic measurements reveal a dramatic rate enhancement for OAT of approximately 24000-fold versus the same reaction for the parent 5-coordinate complex. An Eyring analysis gives H=14kcalmol(-1), S=-10calmol(-1)K(-1). Computational studies fully support the structures, spin states, and relative reactivity of the 5- and 6-coordinate Mn-V(O) complexes.
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