Controlled Dimerization and Bonding Scheme of Icosahedral M@Au12 (M=Pd, Pt) Superatoms

Emi Ito; Shinjiro Takano; Toshikazu Nakamura; Tatsuya Tsukuda

doi:10.1002/anie.202010342

Controlled Dimerization and Bonding Scheme of Icosahedral M@Au₁₂ (M=Pd, Pt) Superatoms

Angew Chem Int Ed Engl. 2021 Jan 11;60(2):645-649. doi: 10.1002/anie.202010342. Epub 2020 Nov 10.

Authors

Emi Ito¹, Shinjiro Takano¹, Toshikazu Nakamura², Tatsuya Tsukuda^{1

3}

Affiliations

¹ Department of Chemistry, Graduate School of Science, The University of Tokyo, 7-3-1 Hongo, Bunkyo-ku, Tokyo, 113-0033, Japan.
² Institute for Molecular Science, Myodaiji, Okazaki, 444-8585, Japan.
³ Elements Strategy Initiative for Catalysts and Batteries (ESICB), Kyoto University, Katsura, Kyoto, 615-8520, Japan.

PMID: 33006224
DOI: 10.1002/anie.202010342

Abstract

Targeted syntheses of MM'Au₃₆ (PET)₂₄ (M, M'=Pd, Pt; PET=SC₂ H₄ Ph) were achieved by hydride-mediated fusion reactions between [MAu₈ (PPh₃ )₈ ]²⁺ and [M'Au₂₄ (PET)₁₈ ]^- . Single-crystal X-ray diffraction analysis indicated that the products have bi-icosahedral MM'Au₂₁ cores composed of M@Au₁₂ and M'@Au₁₂ superatoms. Although the MM'Au₂₁ superatomic molecules correspond to O₂ in terms of the number of valence electrons (12 e), the distances between the icosahedrons were larger than that in the bi-icosahedral Au₂₃ core of Au₃₈ (PET)₂₄ corresponding to F₂ and the spin state was singlet. These counterintuitive results were explained by a "bent bonding model" based on tilted (non-orthogonal) bonding interaction between the 1P superatomic orbitals of M@Au₁₂ and M'@Au₁₂ superatoms.

Keywords: cluster compounds; dimerization; gold; superatomic molecules; superatoms.

Abstract

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