Chemistry of the metal carbonyls. Part 75. Synthesis of aquatetracarbonyl(triphenylphosphine)manganese tetrafluoroborate and related cationic tetracarbonylmanganese complexes

Abstract

The complex [MnMe(CO)₄(PPh₃)] reacts with [CPh₃][BF₄] in wet dichloromethane to give the salt cis-[Mn(CO)₄(OH₂)(PPh₃)][BF₄]. The same aqua-cation is obtained on treating [MnR(CO)₄(PPh₃)](R = H, Ph, or COMe) with [CPh₃][BF₄] under similar conditions, or by treating [MnR(CO)₄(PPh₃)](R = Me or Br) or [[graphic omitted]Ph₂)}(CO)₄] with [OMe₃][BE₄] in dichloromethane. The related cations cis-[Mn(CO)₄(OH₂)(PR₃)]⁺[PR₃= PEt₃, PMe₂Ph, PMePh₂ or PPh(OMe)₂] are also reported. The complex [MnMe(CO)₄(PPh₃)] reacts with [CPh₃][BF₄] in acetonitrile to give the salt [Mn(CO)₄(NCMe)(PPh₃)][BF₄]. The aqua-ligand in [Mn(CO)₄(OH₂)(PPh₃)]⁺ is readily replaced to give the species [Mn(CO)₄L(PPh₃)]⁺(L = C₅H₅N, CNBu^t, CH₂:CNCN, SMe₂, H₂S, PPh₃, or CO).