Organometallic probe for the electronics of base-stabilized group 11 metal cations

Braunschweig, Holger, Ewing, William C, Kramer, Thomas, Mattock, James D, Vargas, Alfredo and Werner, Christine (2015) Organometallic probe for the electronics of base-stabilized group 11 metal cations. Chemistry - A European Journal, 21 (35). pp. 12347-12356. ISSN 0947-6539

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A number of trimetalloborides have been synthesized through the reactions of base-stabilized coinage metal chlorides with a dimanganaborylene lithium salt in the hope of using this organometallic platform to compare and evaluate the electronics of these popular coinage metal fragments. The adducts of CuI, AgI, and AuI ions, stabilized by tricyclohexylphosphine (PCy3), N-1,3-bis(4-methylphenyl)imidazol-2-ylidene (ITol), or 1-(2,6-diisopropylphenyl)-3,3,5,5-tetramethylpyrrolidin-2-ylidene (CAAC), with [{Cp(CO)2Mn}2B]− were studied spectroscopically, structurally, and computationally. The geometries of the adducts fall into two classes, one symmetric and one asymmetric, each relying on the combined characteristics of both the metal and ligand. The energetic factors proposed as the causes of the structural differences were investigated by ETS-NOCV (extended transition state-natural orbitals for chemical valence) analysis, which showed the final geometry to be controlled by the competition between the tendency of the coinage metal to adopt a higher or lower coordination number and the willingness of the cationic fragment to participate in back-bonding interactions.

Item Type: Article
Schools and Departments: School of Life Sciences > Chemistry
Subjects: Q Science > QD Chemistry
Depositing User: Alfredo Vargas
Date Deposited: 22 Jul 2015 09:04
Last Modified: 28 Jul 2017 14:56

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