The synthesis of the intrafaujasite anchoring of ruthenium carbonyl cl
usters involves the adsorption of metal carbonyl species or metal ion
exchange into faujasite cages followed by reductive carbonylation unde
r an atmosphere of CO and H-2. The characterization of the structure a
nd properties of these samples was based on a multianalytical approach
, including FT-IR, UV-vis, PXRD, and EXAFS spectroscopies, CO/H-2 gas
chemisorption, and (CO)-C-13 isotopic exchange. From this study, sever
al key points emerge. (a) [Ru-3(CO)(12)] clusters thermally diffused i
nto dehydrated faujasite cages. (b) [Ru-3(CO)(12)] guests in Na56Y wer
e thermally activated, in a hydrogen atmosphere, generating intrafauja
site [H4Ru4(CO)(12)]. (c) Hexammineruthenium(III) complexes in Na56X a
nd Na56Y underwent progressive thermal activation, in a CO and H-2 atm
osphere. The generation process was considered to occur through conver
sion of the intermediates [Ru(NH3)(5)(CO)](2+) and Ru-1(CO)(3) to [Ru-
6(CO)(18)](2-). (d) A rapid (CO)-C-13/ (CO)-C-12 isotopic exchange was
found to reversibly occur for [Ru-6(CO)(18)](2-)/Na56X under H-2 coex
istence. (e) Internal and external confinement of ruthenium carbonyl c
lusters were compared. (f) Oxidation fragmentation under an O-2 atmosp
here and reductive regeneration under a CO and H-2 atmosphere were fou
nd to reversibly occur for [Ru-6(CO)(18)](2-) guests. (g) Intrafaujasi
te anchoring of ruthenium carbonyl clusters showed a strong interactio
n with the extraframework Na+ alpha-cage cations, through involvement
of the oxygen end of the bridging or equatorial terminal carbonyl liga
nds.