Stabilities, Electronic Structures, and Bonding Properties of Iron Complexes (E(1)E(2))Fe(CO)(2)(CNAr(Tripp2))(2) (E(1)E(2)=BF, CO, N(2), CN(−), or NO(+))

The coordination of 10‐electron diatomic ligands (BF, CO N(2)) to iron complexes Fe(CO)(2)(CNAr(Tripp2))(2) [Ar(Tripp2)=2,6‐(2,4,6‐(iso‐propyl)(3)C(6)H(2))(2)C(6)H(3)] have been realized in experiments very recently (Science, 2019, 363, 1203–1205). Herein, the stability, electronic structures, and bonding properties of (E(1)E(2))Fe‐(CO)(2)(CNAr(Tripp2))(2) (E(1)E(2)=BF, CO, N(2), CN(−), NO(+)) were studied using density functional (DFT) calculations. The ground state of all those molecules is singlet and the calculated geometries are in excellent agreement with the experimental values. The natural bond orbital analysis revealed that Fe is negatively charged while E(1) possesses positive charges. By employing the energy decomposition analysis, the bonding nature of the E(2)E(1)–Fe(CO)(2)(CNAr(Tripp2))(2) bond was disclosed to be the classic dative bond E(2)E(1)→Fe(CO)(2)(CNAr(Tripp2))(2) rather than the electron‐sharing double bond. More interestingly, the bonding strength between BF and Fe(CO)(2)(CNAr(Tripp2))(2) is much stronger than that between CO (or N(2)) and Fe(CO)(2)(CNAr(Tripp2))(2), which is ascribed to the better σ‐donation and π back‐donations. However, the orbital interactions in CN(−)→Fe(CO)(2)(CNAr(Tripp2))(2) and NO(+)→Fe(CO)(2)(CNAr(Tripp2))(2) mainly come from σ‐donation and π back‐donation, respectively. The different contributions from σ donation and π donation for different ligands can be well explained by using the energy levels of E(1)E(2) and Fe(CO)(2)(CNAr(Tripp2))(2) fragments.