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

Abstract

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 TlPF₆ to give [(thf)₂Tl(µ-NC)Mn(CO)(dppm)₂][PF₆] 1, [{Tl(µ-NC)MnL_x}₂][PF₆]₂ [L_x = cis-(CO)₂{P(OR)₃}(dppm), R = Ph 2 or Et 3] and [Tl{(µ-NC)MnL_x}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 µ₃-κC∶κN∶κN cyanide ligand N-bonded to two thallium atoms and C-bonded to manganese.