Lewis Acid Assisted Nitrate Reduction with Biomimetic Molybdenum Oxotransferase Complex

Inorg Chem. 2018 Mar 5;57(5):2594-2602. doi: 10.1021/acs.inorgchem.7b02956. Epub 2018 Feb 14.

Abstract

The reduction of nitrate (NO3-) to nitrite (NO2-) is of significant biological and environmental importance. While MoIV(O) and MoVI(O)2 complexes that mimic the active site structure of nitrate reducing enzymes are prevalent, few of these model complexes can reduce nitrate to nitrite through oxygen atom transfer (OAT) chemistry. We present a novel strategy to induce nitrate reduction chemistry of a previously known catalyst MoIV(O)(SN)2 (2), where SN = bis(4- tert-butylphenyl)-2-pyridylmethanethiolate, that is otherwise incapable of achieving OAT with nitrate. Addition of nitrate with the Lewis acid Sc(OTf)3 (OTf = trifluoromethanesulfonate) to 2 results in an immediate and clean conversion of 2 to MoVI(O)2(SN)2 (1). The Lewis acid additive further reacts with the OAT product, nitrite, to form N2O and O2. This work highlights the ability of Sc3+ additives to expand the reactivity scope of an existing MoIV(O) complex together with which Sc3+ can convert nitrate to stable gaseous molecules.

MeSH terms

  • Biomimetic Materials / chemistry*
  • Biomimetic Materials / metabolism
  • Lewis Acids / chemistry*
  • Lewis Acids / metabolism
  • Molecular Structure
  • Molybdenum / chemistry*
  • Molybdenum / metabolism
  • Nitrates / chemistry*
  • Nitrates / metabolism
  • Organometallic Compounds / chemistry*
  • Organometallic Compounds / metabolism
  • Oxidation-Reduction
  • Oxidoreductases / chemistry*
  • Oxidoreductases / metabolism

Substances

  • Lewis Acids
  • Nitrates
  • Organometallic Compounds
  • Molybdenum
  • Oxidoreductases
  • dimethylsulfide - acceptor oxidoreductase