Formation and reactions of cyanocyclohexadienyl complexes of manganese(I)
- 1 January 1973
- journal article
- research article
- Published by Royal Society of Chemistry (RSC) in J. Chem. Soc., Dalton Trans.
- No. 6,p. 622-626
- https://doi.org/10.1039/dt9730000622
Abstract
Reactions of the cationic arene complexes [(C6H6 –nMen)Mn(CO)3]+ with cyanide ion under mild conditions yield exo-cyanocyclohexadienyl complexes (C6H6 –nMenCN)Mn(CO)3 in which the cyano-group is attached to an unsubstituted carbon atom: the hexamethylbenzene complex reacts differently to form (C6Me6)Mn(CO)2CN. The preference for addition to an unsubstituted carbon atom is (at least in part) kinetic rather than thermodynamic in origin, since the compound formed by cyanide addition to the mesitylene complex rearranges in chloroform solution to give some of the isomer in which the cyano-group is attached to a methyl-substituted carbon atom. Decomposition of the cyanocyclohexadienyl complexes in the solid state or in solution yields either (C6H6 –nMen)Mn(CO)2CN or free arene and a polymeric manganese complex according to the reaction conditions used. Conventional hydride-abstracting reagents remove the cyano-group from the complexes, regenerating [(C6H6 –nMen)Mn(CO)3]+, but oxidation with cerie ion liberates the cyano-arene C6H5 –nMenCN uncontaminated by C6H6 –nMen .Keywords
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