This contribution reports on the insertion of CO2 into actinide methyl and hydride bonds to yield acetate and formate complexes, respectively. Thus, addition of excess CO2 to Cp′2MMe2 (Cp′ = η5- C5Me5, M = Th, U) results in the formation of Cp′2- M(OAc)2 complexes in high yield. These new complexes, which could also be prepared from Cp′2- MCl2 and 2 equiv. of NaOAc, were characterized by standard techniques. On the basis of infrared data and molecular weight measurements the bis(acetate) compounds are suggested to be monomeric with two bidentate acetate ligands, thus achieving a 10-coordinate geometry about the metal ion. The addition of only 1 equiv. of CO2 to Cp′2MMe2 yields Cp′2MMe(OAc) complexes exclusively, suggesting that the formation of the bis(acetate) complexes proceeds sequentially. These complexes could also be prepared via metathesis of the corresponding Cp′2MMeCl complexes with NaOAc. Although the reaction of CO2 with [Cp′2Th(μ-H)(H)]2 produces a variety of uncharacterizable products, Cp′2Th(O2CH)(OCH-t-Bu) was formed upon treatment of Cp′2Th(H)(OCH-t-Bu) with CO2.
ASJC Scopus subject areas
- Physical and Theoretical Chemistry
- Inorganic Chemistry
- Materials Chemistry