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Synthesis and Properties of "Sandwich" Diimine-Coinage Metal Ethylene Complexes.


ABSTRACT: Synthesis and full characterization of cationic isostructural "sandwich" diimine-coinage metal ethylene complexes are reported. Ethylene self-exchange kinetics proceeds by an associative exchange mechanism for Cu and Au complexes. The fastest ligand exchange was observed for Ag complex 8a. The upper limit of ?G‡, assuming associative ligand exchange, was found to be ca. 5.0 kcal/mol. Ethylene self-exchange in Cu complex 7b proceeds with ?G298‡ = 12.9 ± 0.1 kcal/mol, while the exchange is the slowest in Au complex 9, with ?G298‡ = 16.7 ± 0.1 kcal/mol. Copper complex 7b is unusually stable and can survive in air for years.

SUBMITTER: Klimovica K 

PROVIDER: S-EPMC5019172 | biostudies-literature | 2016 Sep

REPOSITORIES: biostudies-literature

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Synthesis and Properties of "Sandwich" Diimine-Coinage Metal Ethylene Complexes.

Klimovica Kristine K   Kirschbaum Kristin K   Daugulis Olafs O  

Organometallics 20160831 17


Synthesis and full characterization of cationic isostructural "sandwich" diimine-coinage metal ethylene complexes are reported. Ethylene self-exchange kinetics proceeds by an associative exchange mechanism for Cu and Au complexes. The fastest ligand exchange was observed for Ag complex <b>8a</b>. The upper limit of Δ<i>G</i><sup>‡</sup>, assuming associative ligand exchange, was found to be ca. 5.0 kcal/mol. Ethylene self-exchange in Cu complex <b>7b</b> proceeds with Δ<i>G</i><sub>298</sub><sup  ...[more]

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