Majority of the substituents in organic and organometallic chemistry are electron-withdrawing in nature toward substrates/ligands. Even for the most electron-donating neutral substituents such as N,N-dialkyl amino groups, the magnitude of electron donation is only nearly half of the magnitude of electron withdrawal by some of the most withdrawing groups. Therefore, development of highly electron-donating substituents promises the discovery of new chemistry. Density functional theory (DFT) study at the M06L/6-311++G(d,p) level in conjunction with molecular electrostatic potential (MESP) topology analysis unraveled the high electron donating nature of imidazolin-2-imine (X and X ') and imidazolin-2-methylidene (Y and Y ') types of moieties as substituents to benzene, pyridine, phosphine (PR3), and N-heterocyclic carbene (NHC). The MESP minimum (Vmin) is derived for aromatic pi-regions and lone-pair regions of the molecules, and the X-, X '-, Y-, and Y '-substituted systems showed a substantial increase in the negative character of Vmin compared to that of the corresponding unsubstituted systems. Multiple substitutions led to a further increase in the magnitude of Vmin, by 195% for benzene with tri-Y ' substitution, 541% for pyridine with tri-Y substitution, 162% for PH3 with tri-X ' substitution, and 23% for NHC with di-X ' substitution, which suggests the amazing electron donating ability of these substituents. The substituted benzene, pyridine, phosphine, and NHC behaved as very strongly coordinating ligands toward Li+, CuCl, and Cr(CO)3. The coordination energy is proportional to the electron richness of the ligands measured in terms of Vmin. The Vmin serves as an electronic parameter and leads to a priori prediction of the coordination reactivity of the ligands. The recent discovery of the complex of PMeX '' 2 (X '' = imidazolin-2-imine group) with C2 is also rationalized in terms of the high electron donating character of X ''. The substitution with imidazolin-2-imine and imidazolin-2-methylidene moieties suggests a powerful molecular design strategy toward the development of highly electron-rich substrates and ligands.
