George J. P. Britovsek

The facile light‐driven insertion reaction of oxygen into metal carbon bonds of the BPI (1,3‐bis(2‐pyridylimino)isoindole) complexes [Pt(BPI)Me] and [Pd(BPI)Me] has been investigated by LED‐NMR in CDCl 3 . The initial insertion reaction leads to peroxo complexes [Pt(BPI)OOMe] and [Pd(BPI)OOMe], which undergo further reactions over time. Spectra were recorded at 1 minute time intervals, which enabled the tracking of the methyl substituent, which eventually generates formaldehyde (and methanediol) and methanol in almost equal proportions. Degradation of the solvent CDCl 3 to phosgene and DCl in the presence of oxygen and light leads to several side reactions. DCl reacts with [M(BPI)Me] and [M(BPI)OOMe] to form [M(BPI)Cl], whereas phosgene reacts with in situ generated methanol to chloro methylformate and dimethyl carbonate.