Reactions of platinum(iv)-bound nitriles with isomeric nitroanilines: addition vs. substitution†
Abstract
The platinum(IV) complex trans-[PtCl4(EtCN)2] reacts smoothly and under mild conditions with isomeric o-, m- and p-nitroanilines (NAs) yielding two different types of products depending on the NA isomer, viz. the nitroaniline complexes cis/trans-[PtCl4(NA)2] (cis/trans-1–3) and the C(Et)NHC6H4NO2-m}(EtCN)] (4), trans-[PtCl4{NH
C(Et)NHC6H4NO2-m}2] (5) and trans-[PtCl4{NH
C(Et)NHC6H4NO2-p}(EtCN)] (6). Complexes 4 and 5 undergo
C(Et)NHC6H3NO2-m}(EtCN)] (7) and mer-[PtCl3{NH
C(Et)NHC6H4NO2-m}{NH
C(Et)NHC6H3NO2-m}] (8), respectively. Moreover, 8 both in the solid state and in solution undergoes the second step of the cyclometalation, generating [PtCl2{NH
C(Et)NHC6H3NO2-m}2] (9). In 4, the
C(OH)Et}] (10), or methanol addition providing trans-[PtCl4{NH
C(Et)NHC6H4NO2-m}{NH
C(Et)OMe}] (11). All compounds, besides 9, were characterized by C, H, and N elemental analyses, high-resolution