TY - JOUR
T1 - Bioinspired oxidation of oximes to nitric oxide with dioxygen by a nonheme iron(II) complex
AU - Bhattacharya, Shrabanti
AU - Lakshman, Triloke Ranjan
AU - Sutradhar, Subhankar
AU - Tiwari, Chandan Kumar
AU - Paine, Tapan Kanti
N1 - Funding Information:
TKP acknowledges Science and Engineering Research Board (SERB), India, for the financial support (Project: EMR/2014/000972). SB thanks the Department of Science and Technology (DST), Govt. of India, for INSPIRE fellowship, and TRL thanks the Council of Scientific and Industrial Research (CSIR), India, for a research fellowship.
Publisher Copyright:
© 2019, Society for Biological Inorganic Chemistry (SBIC).
PY - 2020/2/1
Y1 - 2020/2/1
N2 - The ability of two iron(II) complexes, [(TpPh2)FeII(benzilate)] (1) and [(TpPh2)(FeII)2(NPP)3] (2) (TpPh2 = hydrotris(3,5-diphenylpyrazol-1-yl)borate, NPP-H = α-isonitrosopropiophenone), of a monoanionic facial N3 ligand in the O2-dependent oxidation of oximes is reported. The mononuclear complex 1 reacts with dioxygen to decarboxylate the iron-coordinated benzilate. The oximate-bridged dinuclear complex (2), which contains a high-spin (TpPh2)FeII unit and a low-spin iron(II)–oximate unit, activates dioxygen at the high-spin iron(II) center. Both the complexes exhibit the oxidative transformation of oximes to the corresponding carbonyl compounds with the incorporation of one oxygen atom from dioxygen. In the oxidation process, the oxime units are converted to nitric oxide (NO) or nitroxyl (HNO). The iron(II)–benzilate complex (1) reacts with oximes to afford HNO, whereas the iron(II)–oximate complex (2) generates NO. The results described here suggest that the oxidative transformation of oximes to NO/HNO follows different pathways depending upon the nature of co-ligand/reductant.
AB - The ability of two iron(II) complexes, [(TpPh2)FeII(benzilate)] (1) and [(TpPh2)(FeII)2(NPP)3] (2) (TpPh2 = hydrotris(3,5-diphenylpyrazol-1-yl)borate, NPP-H = α-isonitrosopropiophenone), of a monoanionic facial N3 ligand in the O2-dependent oxidation of oximes is reported. The mononuclear complex 1 reacts with dioxygen to decarboxylate the iron-coordinated benzilate. The oximate-bridged dinuclear complex (2), which contains a high-spin (TpPh2)FeII unit and a low-spin iron(II)–oximate unit, activates dioxygen at the high-spin iron(II) center. Both the complexes exhibit the oxidative transformation of oximes to the corresponding carbonyl compounds with the incorporation of one oxygen atom from dioxygen. In the oxidation process, the oxime units are converted to nitric oxide (NO) or nitroxyl (HNO). The iron(II)–benzilate complex (1) reacts with oximes to afford HNO, whereas the iron(II)–oximate complex (2) generates NO. The results described here suggest that the oxidative transformation of oximes to NO/HNO follows different pathways depending upon the nature of co-ligand/reductant.
KW - Iron
KW - Nitric oxide
KW - Nonheme
KW - Oxidation
KW - Oximes
UR - http://www.scopus.com/inward/record.url?scp=85074258371&partnerID=8YFLogxK
U2 - 10.1007/s00775-019-01726-6
DO - 10.1007/s00775-019-01726-6
M3 - Article
C2 - 31637527
AN - SCOPUS:85074258371
SN - 0949-8257
VL - 25
SP - 3
EP - 11
JO - Journal of Biological Inorganic Chemistry
JF - Journal of Biological Inorganic Chemistry
IS - 1
ER -