Oxidative demetalation of Fischer alkoxy carbene complexes with stoichiometric pyridine N-oxide and NaBH4-promoted demetalation of Fischer iminocarbene complexes with sulfur and selenium

Oxidation of Fischer alkoxy carbene complexes were systematically investigated with stoichiometric pyridine N-oxide (PNO) under mild conditions, forming ester products in good to excellent yields from the corresponding monocarbene complexes. Fischer alkoxy biscarbene complexes efficiently underwent stepwise oxidative demetalation under controlled conditions, resulting in ester-monocarbene and diester products, respectively. This oxidation protocol has demonstrated a generally efficient method to oxidize Fischer alkoxy carbene complexes under mild conditions, providing a new route to novel monocarbene complexes from Fischer biscarbene complexes. In the presence of NaBH4, reactions of Fischer iminocarbene complexes with elemental sulfur or selenium in ethanol at ambient temperature regioselectively afforded thione or selone complexes by insertion of a sulfur or selenium atom into the Mdouble bond; length as m-dashC bonds in Fischer carbene complexes, and metal-free selone was also obtained. The molecular structures of the iminocarbene complexes and selone derivatives were confirmed by X-ray crystallographic study. The NaBH4-promoted demetalation protocol suggests a potential new route to demetalate Fischer aminocarbene complexes.