A coordination strategy to realize a sextuply-bonded complex
Literature Information
Kazuya Yamaguchi, Shigeyoshi Sakaki
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 Mo2 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 M2 (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 M2 core by the coordination, conserve the six bonding orbitals in the occupied space, and suppress the weight of the δ–δ* 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.
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Physical Chemistry Chemical Physics (PCCP) is an international journal co-owned by 19 physical chemistry and physics societies from around the world. This journal publishes original, cutting-edge research in physical chemistry, chemical physics and biophysical chemistry. To be suitable for publication in PCCP, articles must include significant innovation and/or insight into physical chemistry; this is the most important criterion that reviewers and Editors will judge against when evaluating submissions. The journal has a broad scope and welcomes contributions spanning experiment, theory, computation and data science. Topical coverage includes spectroscopy, dynamics, kinetics, statistical mechanics, thermodynamics, electrochemistry, catalysis, surface science, quantum mechanics, quantum computing and machine learning. Interdisciplinary research areas such as polymers and soft matter, materials, nanoscience, energy, surfaces/interfaces, and biophysical chemistry are welcomed if they demonstrate significant innovation and/or insight into physical chemistry. Joined experimental/theoretical studies are particularly appreciated when complementary and based on up-to-date approaches.

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