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

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

School of Chemistry and Moleculai Engineering

Research output: Contribution to journal › Article › peer-review

11 Scopus citations

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.

Original language	English
Pages (from-to)	17350-17355
Number of pages	6
Journal	Chemistry - A European Journal
Volume	26
Issue number	72
DOIs	https://doi.org/10.1002/chem.202002795
State	Published - 23 Dec 2020

Keywords

carbodicarbene
carbone
double dative bond
metal–metal interaction
palladium

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title = "Carbodicarbene: geminal-Bimetallic Coordination in Selective Manner",

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",

author = "Au-Yeung, {Ka Chun} and Dengmengfei Xiao and Shih, {Wei Chih} and Yang, {Hsiu Wen} and Wen, {Yuh Sheng} and Yap, {Glenn P.A.} and Chen, {Wen Ching} and Lili Zhao and Ong, {Tiow Gan}",

note = "Publisher Copyright: {\textcopyright} 2020 Wiley-VCH GmbH",

year = "2020",

month = dec,

day = "23",

doi = "10.1002/chem.202002795",

language = "英语",

volume = "26",

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T1 - Carbodicarbene

T2 - geminal-Bimetallic Coordination in Selective Manner

AU - Au-Yeung, Ka Chun

AU - Xiao, Dengmengfei

AU - Shih, Wei Chih

AU - Yang, Hsiu Wen

AU - Wen, Yuh Sheng

AU - Yap, Glenn P.A.

AU - Chen, Wen Ching

AU - Zhao, Lili

AU - Ong, Tiow Gan

PY - 2020/12/23

Y1 - 2020/12/23

N2 - 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.

AB - 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.

KW - carbodicarbene

KW - carbone

KW - double dative bond

KW - metal–metal interaction

KW - palladium

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U2 - 10.1002/chem.202002795

DO - 10.1002/chem.202002795

M3 - 文章

C2 - 32537790

AN - SCOPUS:85093112877

SN - 0947-6539

VL - 26

SP - 17350

EP - 17355

JO - Chemistry - A European Journal

JF - Chemistry - A European Journal

IS - 72

ER -

Carbodicarbene: geminal-Bimetallic Coordination in Selective Manner

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Keywords

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