SOLID-STATE REACTIONS OF IRIDIUM-1,5-CYCLOOCTADIENE COMPOUNDS WITH HYDROGEN AND CARBON-MONOXIDE

Solid-gas reactions of [Ir(COD)(PhCN)L]ClO4 (1), [Ir(COD)L2]ClO4 (2), [Ir(H)2(COD)(PhCN)L]ClO4 (3), [Ir(H)2(COD)L2] ClO4 (4), [Ir(COD)(CO)2L ]ClO4 (5), [Ir(COD)(CO)L2]ClO4 (6) and [Ir(COD)(PhCN)2]ClO4 (7) (COD=1 ,5-cyclooctadiene; L=PPh3 (a), AsPh3 (b)) with H-2 and CO have been in vestigated to find the differences in reactivities from those in solut ion. Ir(H). moiety and cyclooctene (COE) are detected in the solid-gas reactions of 1 and 2 with H-2 while they are not observed in the reac tions in solution. Complexes, 3 and 4 lose H-2 in the solid state whil e they undergo hydride transfer to COD in solution to produce COE and cyclooctane (COA). Solid-gas reaction of 5 and 6 with H-2 produce only COE at 25-degrees-C while their reactions in solution produce COA. Th e reaction of CO with 3a in the solid state gives quantitative amount of 5a while in solution it gives only unknown product. Both reactions of 7 in the solid state and in solution with CO give unidentified brow n solid which further reacts with CO/H-2 to give Ir4(CO)12.