Oxidative Coordination versus C3 -C(O)Me Bond Cleavage in Acetylacetonate Iridium Complexes
Christopher E Rivas1, Jose C Alvarado-Monzon1, Gerardo Gonzalez-Garcia1
1Departamento de Química, División de Ciencias Naturales y Exactas, Universidad de Guanajuato, Campus Noria Alta. Noria Alta s/n, Guanajuato, C.P., 36050, Gto., México.
Abstract:
Iridabicycles [Ir{κ3 -N,C,O-(pyC(H)=C(C(O)Me)2 }(Cl)(L-L)](L-L=cod (cod=1,5-cyclooctadiene), 1 a; bipy (bipy=2,2'-bipyridine), 1 b) have been obtained by oxidative coordination of 3-(pyridine-2-yl-methylene)pentane-2,4-dione L1, to the complexes [{Ir(μ-Cl)(cod)}2 ] and [{Ir(μ-Cl)(coe)2 }2 ] (coe=cis-cyclooctene), the latter in the presence of bipy. Remarkably, cleavage of the C3 -C(O)Me bond of L1 has instead been achieved in the reaction with [Ir(Cl)(dmb)2 ] (dmb=2,3-dimethylbutadiene), yielding a compound formulated as [Ir{κ2 -N,C-(pyC(H)C(C(O)Me))}(CO)(μ-Cl)(Me)]2 , 2. Treatment of dimer 2 with DMSO or PMe3 produced the complexes[Ir{κ2 -N,C-(pyC(H)C(C(O)Me)}(CO)Cl(Me)L] (L=DMSO, 3 a; PMe3 , 3 b). Plausible mechanisms for the reactions leading to complexes 1 and 2 are proposed by means of DFT calculations.
Related Concept Videos
Alkynes to Carboxylic Acids: Oxidative Cleavage
Structural Isomerism
Isomers are different chemical species that have the same chemical formula. Structural isomerism of coordination compounds can be divided into two subcategories, the linkage isomers and coordination-sphere isomers.
Linkage isomers occur when the coordination compound contains a ligand that can bind to the transition metal center through two different atoms. For example, the CN− ligand can bind through the carbon atom or through the nitrogen atom. Similarly, SCN− can...
Oxidation of Alkenes: Anti Dihydroxylation with Peroxy Acids
Valence Bond Theory
α-Hydroxy Ketones via Reductive Coupling of Esters: Acyloin Condensation Overview
Coordination Number and Geometry


