97920-25-7Relevant academic research and scientific papers
Intercalation of metal cluster complexes in smectite clay
Giannelis, Emmanuel P.,Pinnavaia, Thomas J.
, p. 3602 - 3607 (2008/10/08)
The cationic metal cluster complexes Ru3(CO)9(P-P+)3, H4Ru4(CO)8(P-P+)4, Ir4(CO)9(P-P+)3, Os3(CO)11(P-P+), and H2Os3(CO)10(P-P+), where P-P+ is the phosphonium-phosphine ligand Ph2P(CH2)2P+Ph2(CH 2Ph), have been synthesized as BF4- salts. On the basis of similarities in IR carbonyl stretching frequencies, the cationic complexes are structurally analogous to neutral analogues containing arylphosphine ligands. The ion-exchange reaction of Na+-hectorite, a typical smectite clay, in aqueous suspension with solutions of the cationic clusters in acetone results in the formation of cluster-clay intercalation compounds with d001 spacings in the range 22-27 ? and gallery heights of 12.5-17.5 ?. H2Os3(CO)9(P-P+)-hectorite, which is formed from H2Os3(CO)10(P-P+)-hectorite by thermal decarbonylation, is the first known example of an intercalated metal cluster catalyst. The longevity of the intercalated cluster for the isomerization of 1-hexene is similar to that of the homogeneous cluster, with approximately 3300 turnovers of the cluster being observed before cessation of activity due to the formation of a coordinatively saturated H2Os3(CO)9(vinylidene)(P-P+) species.
