Conversion of (η⁵-C₅H₅)Co(PPh₃)₂and Nitro Compounds to Mononuclear η¹(<i>N</i>)-Nitrosoalkyl and Dinuclear μ-η¹(<i>N</i>):η²(<i>N</i>,<i>O</i>)-Nitrosoaryl Complexes

Abstract

The room-temperature reaction of (η5-C5H5)Co(PPh3)2 (5) with aliphatic nitro compounds, RNO2, where R = Me, Et, iPr, leads to formation of the corresponding η1-nitroso derivatives (η5-C5H5)Co(PPh3)[η1(N)-N(O)R] (6-Me, R = Me; 6-Et, R = Et; 6-Pr, R = iPr). Aromatic nitro compounds, ArNO2, where Ar = −C6H5, −p-C6H4C⋮CTMS, undergo reaction with 5 to give the μ-η1:η2-nitroso derivatives, [(η5-C5H5)Co]2[μ-η1(N):η2(N,O)-N(O)R]2 (7-Ph, R = −C6H5; 7-Ar, R = −p-C6H4C⋮CTMS). Complexes 6-Me and 7-Ar were characterized by X-ray crystallographic analyses.