Chapter 12 in the book “Bioinspired Catalysis”
Authors: Davinder Kumar and Craig A. Grapperhaus
This chapter highlights selected complexes with tetra- and penta-dentate chelates that provide key insights into the oxidized sulfur environment at the enzyme active site. Small-molecule mimics with variable S-oxidation levels provide an attractive method to address these interactions. It discusses a brief history of metal-thiolate sulfur-oxygenation is provided, followed by selected S-oxygenation studies relevant to nitrile hydratase (NHase). The NHase are divided by metal type and organized according to the donor atoms of the chelates. Several ruthenium catalysts have been reported as nitrile hydration catalysts. Ruthenium is also a logical choice for oxidation studies as the second-row transition metal maintains a consistent low spin, which was found to promote S-oxygenation.
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