A coordination strategy to realize a sextuply-bonded complex

作者：Chen Yue; Hasegawa Jun ya^*; Yamaguchi Kazuya; Sakaki Shigeyoshi^*

来源：Physical Chemistry Chemical Physics, 2017, 19(23): 14947-14954.

DOI：10.1039/c7cp00871f

The synthesis of higher-order multiple bonds is a great challenge in chemistry. However, no stable compound with a sextuple bond has been reported, except for Mo-2 in an inert matrix at low temperatures. Herein, we propose a strategy to construct a sextuple bond in a dinuclear transition metal complex based on complete active space second-order perturbation theory (CASPT2) and density functional theory calculations. When the dinuclear core M-2 (M = W, Mo, and Re+) is capped by two neutral electron-donating ligands at both M-M ends, a sextuple bond can be realized. The proposed ligands stabilize the M-2 core by the coordination, conserve the six bonding orbitals in the occupied space, and suppress the weight of the delta-delta(star) excited electronic configuration. Calculated large formation energies of these complexes indicate the large possibility of the synthesis. Electronic structures and sextuply bonding interactions were analyzed in detail.

• 出版日期2017-6-21