The isolation of the mixed carbonyl/isocyanide analogue to the classic [Mn(CO)5] radical provides access to a diverse range of organometallic one-electron chemistry.  The electronic characteristics of zerovalent Mn(CO)3(CNArDipp2)2 (Dipp = 2,6-(i-Pr)2C6H3) have been probed using room temperature solution state EPR, which shows the radical to be metal centered.  Spin trapping with nitrosoarenes has led to isolable spin-adducts that display an ?2-NO bonding mode with concurrent loss of one equivalent of CO.  It will be shown that contrary to previous spin-trap studies of zerovalent manganese carbonyls, formation of the ?2 adduct is preferential to that of a ?1-N nitrosoarene.  Additionally, reactivity studies demonstrate the ability to access unique Mn(I) complexes through controlled radical coupling of substrates, and provide further corroboration of a metal-localized radical.  A highlight of this chemistry is the formation of a unique dimanganese dimer bridged by carbon disulfide, which we propose to be comparable to the initial intermediate in CO2 electrochemical reduction by group 7 complexes.

Reactivity and electronic characteristics of a zerovalent manganese isocyanide complex

248th National Meeting (2014)

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