Carbodicarbene: geminal-Bimetallic Coordination in Selective Manner
- 23 December 2020
- journal article
- research article
- Published by Wiley in Chemistry – A European Journal
- Vol. 26 (72), 17350-17355
- https://doi.org/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(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 pconjugation 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
Funding Information
- Ministry of Science and Technology, Taiwan (MOST-104-2628-M-001-005-MY4, MOST-108-2113-M-001-026-MY3, MOST-107-2113-M-001-034-MY2)
This publication has 62 references indexed in Scilit:
- Synthetic Modification of Acyclic Bent Allenes (Carbodicarbenes) and Further Studies on Their Structural Implications and ReactivitiesOrganometallics, 2013
- On the metallic nature of carbon in allenes and heterocumulenesDalton Transactions, 2011
- Synthesis and Ligand Properties of Stable Five‐Membered‐Ring Allenes Containing Only Second‐Row ElementsAngewandte Chemie-International Edition, 2008
- Synthesis and Ligand Properties of Stable Five‐Membered‐Ring Allenes Containing Only Second‐Row ElementsAngewandte Chemie, 2008
- Synthesis of an Extremely Bent Acyclic Allene (A “Carbodicarbene”): A Strong Donor LigandAngewandte Chemie-International Edition, 2008
- Synthesis of an Extremely Bent Acyclic Allene (A “Carbodicarbene”): A Strong Donor LigandAngewandte Chemie, 2008
- C(NHC)2: Divalent Carbon(0) Compounds with N‐Heterocyclic Carbene Ligands—Theoretical Evidence for a Class of Molecules with Promising Chemical PropertiesAngewandte Chemie-International Edition, 2007
- C(NHC)2: zweibindige Kohlenstoff(0)-Verbindungen mit N-heterocyclischen Carbenliganden – theoretische Belege für eine Molekülklasse mit vielversprechenden EigenschaftenAngewandte Chemie, 2007
- Carbodiphosphoranes: The Chemistry of Divalent Carbon(0)Angewandte Chemie-International Edition, 2006
- Carbodiphosphorane: die Chemie von zweibindigem Kohlenstoff(0)Angewandte Chemie, 2006