Diversification of the Carbodicarbene Class by Embedding an Anionic Component in its Scaffold

Cheng-Han Yu; Ka-Chun Au-Yeung; Ruiqin Liu; Chao-Hsien Lee; Dandan Jiang; Bamlaku Semagne Aweke; Chia-Hung Wu; Yu-Jou Wang; Ting-Hsuan Wang; Kien Voon Kong; Glenn P A Yap; Wen-Ching Chen; Gernot Frenking; Lili Zhao; Tiow-Gan Ong

doi:10.1002/chem.202302886

Diversification of the Carbodicarbene Class by Embedding an Anionic Component in its Scaffold

Chemistry. 2023 Dec 19;29(71):e202302886. doi: 10.1002/chem.202302886. Epub 2023 Nov 6.

Authors

Cheng-Han Yu¹, Ka-Chun Au-Yeung^{1

2}, Ruiqin Liu³, Chao-Hsien Lee¹, Dandan Jiang³, Bamlaku Semagne Aweke^{1

4

5}, Chia-Hung Wu^{1

6}, Yu-Jou Wang^{1

6}, Ting-Hsuan Wang¹, Kien Voon Kong⁶, Glenn P A Yap⁷, Wen-Ching Chen¹, Gernot Frenking^{3

8}, Lili Zhao³, Tiow-Gan Ong^{1

6

9}

Affiliations

¹ Institute of chemistry, Academia Sinica, Taipei, Taiwan (R.O.C., 115201.
² Corporate R&D Center, LCY Chemical Corporation, Kaohsiung, Taiwan (R.O.C.
³ School of Chemistry and Molecular Engineering, State Key Laboratory of Materials-Oriented Chemical Engineering, Nanjing Tech University, Nanjing, China.
⁴ Department of Applied Chemistry, National Yang Ming Chiao Tung University, Hsinchu, Taiwan (R.O.C.
⁵ Sustainable Chemical Science and Technology, Taiwan International Graduate Program, Academia Sinica, Taipei, Taiwan (R.O.C.
⁶ Department of Chemistry, National Taiwan University, Taipei, Taiwan (R.O.C.
⁷ Department of Chemistry and Biochemistry, University of Delaware, Newark, Delaware, United States.
⁸ Fachbereich Chemie, Philipps-Universität Marburg, Hans-Meerwein-Strasse, D-35043, Marburg, Germany.
⁹ Department of Medicinal and Applied Chemistry, Kaohsiung Medical University, Kaohsiung, Taiwan (R.O.C.

PMID: 37730960
DOI: 10.1002/chem.202302886

Abstract

Carbodicarbene (CDC) has become an emerging ligand in many fields due to its strong σ-donating ability. <We report the first synthesis of the anionic CDC Pd complexes containing a BF₂ ^- moiety within the framework to leverage the electronic feature of carbon carbone. The elucidation of X-ray crystal structures, ligand competition as well as transmetallation experiments suggest that the anionic moiety has enhanced the overall donor strength of the traditional neutral CDC. Importantly, this anionic scaffold exhibits a facile second coordination toward Au(I), Ag(I) and Pd(II) without any external ligand assistance, whereas previously reported neutral pincer CDC complexes do not possess a two-fold donor capacity. The analysis of the bonding situation via theoretical methods shows that the description of the anionic CDC moieties in terms of dative bonding is preferred over the model of delocalized positive charge, as it accounts for the two-fold donor ability of the divalent carbon atom, preserving a characteristic feature of a carbone.

Keywords: Anionic carbodicarbene; carbone; dative bonding model; geminal bimetallic complexes.

Abstract

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