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Carbodicarbene: geminal ‐Bimetallic Coordination in Selective Manner
Author(s) -
AuYeung KaChun,
Xiao Dengmengfei,
Shih WeiChih,
Yang HsiuWen,
Wen YuhSheng,
Yap Glenn P. A.,
Chen WenChing,
Zhao Lili,
Ong TiowGan
Publication year - 2020
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.202002795
Subject(s) - geminal , chemistry , bimetallic strip , intramolecular force , valence (chemistry) , valence bond theory , ligand (biochemistry) , palladium , stereochemistry , crystallography , computational chemistry , molecular orbital , molecule , catalysis , organic chemistry , biochemistry , receptor
The reaction of Pd(OAc) 2 with free carbodicarbene (CDC) generates a Pd acetate trinuclear complex 1 via intramolecular C(sp 3 )−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.