Carbodicarbene: geminal-Bimetallic Coordination in Selective Manner

Ka-Chun Au-Yeung; Dengmengfei Xiao; Wei-Chih Shih; Hsiu-Wen Yang; Yuh-Sheng Wen; Glenn P A Yap; Wen-Ching Chen; Lili Zhao; Tiow-Gan Ong

doi:10.1002/chem.202002795

Carbodicarbene: geminal-Bimetallic Coordination in Selective Manner

Chemistry. 2020 Dec 23;26(72):17350-17355. doi: 10.1002/chem.202002795. Epub 2020 Oct 22.

Authors

Affiliations

¹ Institute of Chemistry, Academia Sinica, Taipei, Taiwan.
² Institute of Advanced Synthesis, School of Chemistry and Molecular Engineering, Nanjing Tech University, Nanjing, P.R. China.
³ Department of Chemistry & Biochemistry, University of Delaware, USA.
⁴ Department of Applied Chemistry, National Chiao Tung University, Taipei, Taiwan.
⁵ Department of Chemistry, National Taiwan University, Taipei, Taiwan.

PMID: 32537790
DOI: 10.1002/chem.202002795

Abstract

The reaction of Pd(OAc)₂ with free carbodicarbene (CDC) generates a Pd acetate trinuclear complex 1 via intramolecular C(sp³ )-H bond activation at one of the CDC methyl side arms. The solid structure of 1 reveals the capability of CDC to facilitate a double dative bond with two palladium centers in geminal fashion. This is attributed to the chelating mode of CDC, which can frustrate π-conjugation within the CDC framework. Such effect maybe also amplified by ligand-ligand interaction. The formation of other gem-bimetallic Pd-Pd, Pd-Au, and Ni-Au provides further structural evidence for this proof-of-concept in selective installation. Structural analysis is supported by computational calculations based on state-of-the-art energy decomposition analysis (EDA) in conjunction with natural orbitals for chemical valence (NOCV) method.

Keywords: carbodicarbene; carbone; double dative bond; metal-metal interaction; palladium.

Abstract

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