Merging organometallic chemistry with polyoxometalate chemistry

A series of polyoxomolybdate-incorporated organometallic complexes has been obtained by reaction of [MBr(CO)(5)] or solvated (M(CO)(3)}(+) ions (M = M n or Br) with (nBu(4)N)(2)[Mo2O7] in methanol, sometimes in the presence of triols of the type RC(CH2OH)(3) (R = Me or CH2OH). Their molecular structu res are related to those of previously described polyoxoalkoxomolybdates th rough the formal replacement of fac(MoO2(OR)}(+) units by topologically equ ivalent fac-{M(CO)(3)}(+) units. Representative pairs of structurally relat ed clusters include [Mo2O6(OMe)(4){Re(CO)(3)}(2)](2-) and [Mo4O10(OMe)(6)]( 2-) [Mo2O4{MeC(CH2O)(3)}(2){Mn(CO)(3)}](-)and [Mo3O6(OMe){MeC(CH2O)(3)}(2)] (-),[Mo2O4 {HOCH2C(CH2O)(3)}(2){Mn(CO)(3)}(2)] and [Mo4O8(OEt)(2){MeC(CH2O) (3)}(2)], [Mo6O16(OMe)(2){MeC(CH2O)(3)}(2-) {Mn(CO)(3)}(2)](2) and [Mo8O20( OMe)(4)-{MeC(CH2O)(3)}(2)](2-). Although the frameworks of the majority of derivatives are based on tetranuclear units which display the common rhomb- like structure, the alternative cubane-type arrangement is observed in [Mo2 O5(OMe)(5)(M(CO)(3)}(2)](-).