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. 2021 Jun 10;27(33):8468-8472.
doi: 10.1002/chem.202100709. Epub 2021 May 13.

Oxidative Coordination versus C3 -C(O)Me Bond Cleavage in Acetylacetonate Iridium Complexes

Christopher E Rivas  1 , Jose C Alvarado-Monzon  1 , Gerardo Gonzalez-Garcia  1 , J Oscar C Jimenez-Halla  1 , Jesus Rangel-Garcia  1 , Crispin Cristobal  1 , Jorge A Lopez  1
Affiliations

Oxidative Coordination versus C3 -C(O)Me Bond Cleavage in Acetylacetonate Iridium Complexes

Christopher E Rivas et al. Chemistry. .

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.

Keywords: C−C bond cleavage; coordinative oxidation; iridabicycles.

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