Nature of the Three-Electron Bond.

We analyze the properties of 15 3-electron bonds, which include σ-3-electron-bonds, such as dihalide radical anions and di-noble gas radical cations, π-3-electron-bonds as in hydrazine radical cations, and doubly-π-(3e)-bonded species such as O2 , FeO+ , S2 , etc. The primary analytical tool is the breathing-orbital valence-bond (BOVB) method, which enables us to quantify the charge shift resonance energy (RECS ) of the three electrons, and the bond dissociation energies (De ). BOVB is tested reliable against MRCI calculations. Our findings show that in all 3-electron bonds, none of the VB structures have by themselves any bonding. In fact, in each VB structure, the three electrons maintain Pauli repulsion, while the entire bonding energy arises from resonance due to the charge shift between the two or more constituent VB structures. Hence, 3e-bonds are charge shift bonds (CSBs). The CSB character is probed by calculating the Laplacian (L) of the 3e-bond. Thus, much like the CSBs in electron-pair bonds, such as F2 or the central bond in [1.1.1]propellane, here too L is positive, thus showing the excess kinetic energy of the shared density due to the Pauli repulsion in the 3-electron VB structures. The RECS values for 3-electron bonds are invariably larger than the corresponding bond energies. For the doubly-π-(3e)-bonded species, RECS is very large, exceeding 100 kcal mol-1 . As such, it is fitting to conclude that σ- and π-3-electron-bonds find their natural place in the CSB family along with two-electron CSBs, with which they share identical energetic and topological characteristics. Experimental manifestations/tests of 3e-CSBs are proposed.