σ versus π-radical: Tuning the electronic nature of neutral carbon (I) compounds with three non-bonding electrons.

The bonding and reactivity of the hypo-coordinated compounds with one, two, and four non-bonding electrons namely, carbon-centered free radical, carbenes, and carbones were well earlier established. Here, we report stability, bonding and reactivity of compounds RCL, where R is one-electron donor group (R = CH 3 (a), CHO (b), and NO 2 (c)) and L is two-electron donor ligand (L = cAAC (1), CO (2), NHC (3) and PMe 3 (4)), having three non-bonding electrons. The ground states of molecules exist in a doublet with a lone pair of electrons and an unpaired electron at the central carbon atom (C1). The spin hops over from π- to σ-type orbitals is observed as the π-acceptor strength of the donor ligand increases. The replacement of the methyl group by CHO and NO 2 indicate that the cAAC and CHO substituted compounds gives a σ-radical except in compound 2c. These molecules show very high proton affinity and exothermic reaction energy for the hydrogen atom addition indicating dual reactivity namely, radical and lone pair reactivity.