Novel N-bound thallium(I) complexes of redox-active cyanomanganese carbonyl ligands:: cyanide as a μ3-κC:κN:κN triply bridging ligand

The cyanomanganese carbonyls trans-[Mn(CN)(CO)(dppm)(2)], and cis- and trans-[Mn(CN)(CO)(2){P(OR)(3)}(dppm)] (R = Ph or Et, dppm = Ph2PCH2PPh2) react with TIPF6 to give [(thf)(2)Tl(mu-NC)Mn(CO)(dppm)(2)][PF6] 1, [{TI(mu-NC)MnLx}(2)][PF6](2) [L-x = cis-(CO)(2){P(OR)(3)}(dppm), R = Ph 2 or Et 3] and [Tl{(mu-NC)MnLx}(2)][PF6] [L-x = trans-(CO)(2){P(OR)(3)}(dppm), R = Ph 4 or Et 5] respectively. Complexes 1 and 3 have been structurally characterised by single-crystal X-ray diffraction methods; the former is pyramidal at thallium while the latter provides a rare example of a mu(3)-kappa C:kappa N:kappa N cyanide ligand N-bonded to two thallium atoms and C-bonded to manganese.