New mixed carbonyl–nitro and –nitrito complexes of manganese and rhenium
Abstract
Treatment of [Mn(CO)5Cl] with Me3NO in CH2Cl2 in the presence of [N(PPh3)2][NO2] gave the anion cis-[Mn(CO)4(NO2)2]– which, on further reaction, yielded the new dianionic trimer [Mn3(CO)6(µ-NO2)4-(µ-ONO)2]2- containing both bridging nitro- and nitrito-groups. Reactions of [Mn2(CO)8(µ-Cl)2], cis-[Mn-(CO)4Cl2]–, [Mn2(CO)6(µ-Cl)3]– or [Mn(CO)3Cl3]2- with [N(PPh3)2][NO2] also produce the same final product. The crystal and molecular structure of the [N(PPh3)2]+ salt has been established by X-ray diffraction analysis. The molecule [N(PPh3)2]2[Mn3(CO)6(µ-NO2)4(µ-ONO)2] crystallises in the triclinic space group P. Addition of [N(PPh3)2][NO2] to [Re(CO)5Cl] in CH2Cl2 yielded a series of mixed carbonyl–nitro/nitrito isomers, which have been characterised in solution. The unusual complex salt [NMe3(CH2Cl)]3[fac-Re(CO)3(NO2)2Cl]Cl has been characterised in the solid state by single-crystal X-ray diffraction methods. The molecule crystallises in the monoclinic space group P21/a.