Intrazeolite anchoring of [HRuCo_3(CO)_9(#mu#_2-CO)_3]: Synthesis and reversible decarbonylation

摘要

The synthesis of intrazeolite anchoring of [HruCo_3(CO)_9(#mu#_2-CO)_3] involves the adsorption of metal carbonyl species into zeolite cages followed by reductive carbonylation under a mixed CO and H_2 atmosphere. The physicochemical characterization of the samples was based on a multianalytical approach, including Fourier transform-infrared, extended x-ray absorption fine structure spectroscopies, and CO/H_2 gas chemisorption. The research encomassed several key points as follows: (a) The generation process of bimetallic carbonyl clusters was considered to occur through the interaction of [Ru-Co], Co(CO)_4~- and Ru~I carbonyls, and conversion into [HRuCo_3(CO)_9(#mu#_3-CO)_3] and further to [HRuCo_3(CO)_9(#mu#_2-CO)_3] isomer. (b) There is significant bimetallic interaction. (c) Internal and external confinement of [HRuCo_3(CO)_9(#mu#_2-CO)_3] were compared. (d) The intrazeolite anchoring of [RuCo_3] carbonyl clusters shows a strong reaction with the extraframework Na~+ #alpha#-cage cations, through involvement of the oxygen end of the bridging carbonyl ligands.