Solid State Reactions of Iridium-1,5-Cyclooctadiene Compounds with Hydrogen and Carbon Monoxide

摘要

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 H2 and CO have been investigated to find the differences in reactivities from those in solution. Ir(H)n moiety and cyclooctene (COE) are detected in the solid-gas reactions of 1 and 2 with H2 while they are not observed in the reactions in solution. Complexes, 3 and 4 lose H2 in the solid state while they undergo hydride transfer to COD in solution to produce COE and cyclooctane (COA). Solid-gas reaction of 5 and 6 with H2 produce only COE at 25∩ while their reactions in solution produce COA. The 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 brown solid which further reacts with CO/H2 to give Ir4(CO)12.