Catalytic activity of dicationic platinum(II) and rhodium(II) complexes towards 9-diazofluorene

9-Diazofluorene (DAF) is catalytically decomposed at 25°C in CH2Cl2 in the presence of 1 mol% of the dicationic platinum(II) complex cis-[Pt(PPh3)2(CH3CN)2][BF4]2 (1) to give the olefin product 9,9′-bifluorenylidene in high yield. Furthermore, DAF undergoes an insertion reaction into the O–H bond of methanol at 25°C in CH2Cl2/MeOH (DAF/MeOH molar ratio 1/20) in the presence of 1 mol% of 1 to give 9-methoxyfluorene in excellent yield. With neutral or cationic dirhodium(II) complexes as catalysts the same reaction yields further products, suggesting the existence of different parallel reaction pathways.