Exceptionally Long (> or =2.9 A) CC bonding interactions in pi-[TCNE]2(2-) dimers: two-electron four-center cation-mediated CC bonding interactions involving pi* electrons.

Three groups of singlet ground state [TCNE](2) (2-) (TCNE=tetracyanoethylene) dimers with characteristic intradimer CC separations (r) and dihedral angles (d) [i.e., group S(t) (r approximately 1.6 A; d=180 degrees ), L(t) (r approximately 3.5 A; d=180 degrees ), and L(c) (r approximately 2.9 A; d= approximately 0 degrees ); notation: S/L: short/long bond length; subscript t/c: trans/cis, respectively] are experimentally characterized. The S(t) group is comprised of sigma-dimers of [TCNE](.-) and octacyanobutanediide, [C(4)(CN)(8)](2-), which have a typical, albeit long, sp(3)-sp(3) sigma bond (r approximately 1.6 A) between each [TCNE](.-) moiety and characteristic nu(CN), nu(CC), and delta(CCN) IR absorptions. The L groups are structurally characterized as pi-dimers of [TCNE](.-) that are either eclipsed with r approximately 2.9 A (L(c)) and the nitriles bend away from the nominal TCNE plane away from the center of the dimer by 5.0 degrees (approximately sp(2.17)) or are noneclipsed with r approximately 3.5 A (L(t)) and the nitriles bend toward the center of the dimer by 1.9 degrees ( approximately sp(2.06)). Ab initio computations on isolated dimers were used to study the formation and stability of these exceptionally long CC (> or =2.9 A) bonding interactions as well as the process of pi-[TCNE](2) (2-) dimer formation for the L(c) and L(t) groups. The results of these computational studies show that the ground-state potential curve is that of a closed-shell/open-shell singlet, depending on the distance. The short S(t) group (r approximately 1.6 A) of dimers in this surface are true minimum-energy structures; however, the L(t) and L(c) groups are unstable, although two different nonphysical minima are found when imposing a double occupancy of the orbitals. These minima are metastable relative to dissociation into the isolated [TCNE](.-) units. Consequently, the existence of dimer dianions in crystals is due to cation.[TCNE](-) interactions, which provide the electrostatic stabilization necessary to overcome the intradimer electrostatic repulsion. This cation-mediated pi*-pi* [TCNE](-).[TCNE](-) interaction complies with Pauling's definition of a chemical bond. This bonding interaction involves the pi* orbitals of each fragment, and arise from the overlap of the b(2g) SOMO on each of the two [TCNE](.-)s to form a filled b(2u) [TCNE](2) (2-) orbital. Although a pi dimer typically forms, if the fragments are close enough a sigma dimer can form. Due to the presence of cation-mediated intradimer CC bonding interactions the L(c) group of pi-[TCNE](2) (2-) dimers exhibits experimentally observable nu(CN) IR absorptions at 2191+/-2 (m), 2173+/-3 (s), and 2162+/-3 cm(-1) (s) and nu(CC) at 1364+/-3 cm(-1) (s) as well as a new UV-Vis feature in the range of 15 000 to 18 200 cm(-1) (549 to 667 nm) and averaging 16 825+/-1180 cm(-1) (594 nm) assigned to the predicted new intradimer (1)A(1g) --> (1)B(1u) transition and is purple on reflected light. Upon cooling to 77 K in 2-methyl tetrahydrofuran, this new band occurs at 18 940 cm(-1) (528 nm) for [[Et(4)N](+)](2)[TCNE](2) (2-), and the yellow solution turns deep red. Group L(t) is characterized by nu(CN) absorptions at 2215+/-2, 2197+/-3, and 2180+/-4 cm(-1) and nu(CC) at 1209+/-9 cm(-1) (w), while group S(T) has nu(CN) bands at 2215+/-4, 2157+/-3, and 2107+/-4 cm(-1) and nu(CC) at 1385+/-1 cm(-1) (vs).