Cyclic Diplatinum Complex with a Tröger's Base Ligand and Reductive Elimination of a Highly Strained Ring Molecule

Yoshigoe, Yusuke; Suzaki, Yuji; Osakada, Kohtaro

doi:10.1002/zaac.202100085

Cited by 2 publications

(1 citation statement)

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“…There were several reports on the exchange reaction of M–C σ-bonds (M = Pt(II), Pd(II), Au(I), etc.) (see supporting Scheme S3b), − and the reactions were generally regarded as a slow process compared to those of the noncovalent metal–ligand bonds, that is, Pd–N and Pt–N bonds (see Scheme S3a). However, the exchange reactions involving aryl–Au(I) complexes have never been reported to date. − …”

Section: Resultsmentioning

confidence: 99%

Dynamic Au–C σ-Bonds Leading to an Efficient Synthesis of [n]Cycloparaphenylenes (n = 9–15) by Self-Assembly

Yoshigoe

Tanji

Hata

et al. 2022

JACS Au

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The transmetalation of the digold(I) complex [Au 2 Cl 2 (dcpm)] ( 1 ) (dcpm = bis(dicyclohexylphosphino)methane) with oligophenylene diboronic acids gave the triangular macrocyclic complexes [Au 2 (C 6 H 4 ) x (dcpm)] 3 ( x = 3, 4, 5) with yields of over 70%. On the other hand, when the other digold(I) complex [Au 2 Cl 2 (dppm)] ( 1′ ) (dppm = bis(diphenylphosphino)methane) was used, only a negligible amount of the triangular complex was obtained. The control experiments revealed that the dcpm ligand accelerated an intermolecular Au(I)–C σ-bond-exchange reaction and that this high reversibility is the origin of the selective formation of the triangular complexes. Structural analyses and theoretical calculations indicate that the dcpm ligand increases the electrophilicity of the Au atom in the complex, thus facilitating the exchange reaction, although the cyclohexyl group is an electron-donating group. Furthermore, the oxidative chlorination of the macrocyclic gold complexes afforded a series of [ n ]cycloparaphenylenes ( n = 9, 12, 15) in 78–88% isolated yields. The reorganization of two different macrocyclic Au complexes gave a mixture of macrocyclic complexes incorporating different oligophenylene linkers, from which a mixture of [ n ]cycloparaphenylenes with various numbers of phenylene units was obtained in good yields.

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