Bioinspired organometallic chemistry*

Abstract: Given the stability of the bond between a mercaptide ligand and various redox-active metals, it is of interest that Nature has evolved significant metalloenzymatic processes that involve key interactions of sulfur-containing functionalities with metals such as Ni, Co, Cu, and Fe. From a chemical perspective, it is striking that these metals can function as robust biocatalysts in vivo, even though they are often “poisoned ” as catalysts in vitro through for-mation of refractory metal thiolates. Insight into the nature of this chemical discrepancy is under study in order to open new procedures in synthetic organic and organometallic chem-istry. INTRODUCTION AND BACKGROUND The highly discriminating activation of a stable carbon–sulfur moiety in the presence of a vast sea of oxygen and nitrogen heteroatoms plays a key role in a number of biochemical transformations [1–5]. To accomplish this task, Nature relies on the use of thiophilic metals such as Ni to achieve the selective activation of a soft, polarizable C–S substrate in a hard environment [6]. It is also significant that