New mixed carbonyl-nitro and -nitrito complexes of manganese and rhenium

Treatment of [Mn(CO)(5)Cl] with Me(3)NO in CH2Cl2 in the presence of [N(PPh(3))(2)][NO2] gave the anion cis-[Mn(CO)(4)(NO2)(2)](-) which, on further reaction, yielded the new dianionic trimer [Mn-3(CO)(6)(mu-NO2)(4)-(mu-ONO)(2)](2-) containing both bridging nitro- and nitrito-groups. Reactions of [Mn-2(CO)(8)(mu-Cl)(2)], cis-[Mn-(CO)(4)Cl-2](-), [Mn-2(CO)(6)(mu-Cl)(3)](-) or [Mn(CO)(3)C1(3)](2-) with [N(PPh(3))(2)][NO2] also produce the same final product. The crystal and molecular structure of the [N(PPh(3))(2)](+) salt has been established by X-ray diffraction analysis. The molecule [N(PPh(3))(2)](2)[Mn-3(CO)(6)(mu-NO2)(4)(mu-ONO)(2)] crystallises in the triclinic space group <P(1)over bar>. Addition of [N(PPh(3))(2)][NO2] to [Re(CO)(5)Cl] in CH2Cl2 yielded a series of mixed carbonyl-nitro/nitrito isomers, which have been characterised in solution. The unusual complex salt [NMe(3)(CH2Cl)](3)[fac-Re(CO)(3)(NO2)(2)Cl]Cl has been characterised in the solid state by single-crystal X-ray diffraction methods. The molecule crystallises in the monoclinic space group P2(1)/a.