By Ivan Bernal (Eds.)
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Similar catalytically active mononuclear species are probably formed from both the metal chlorides and the cluster compounds . High activities were also observed C o 2R h 2( C O ) 12 (8 ) and Co3 R h ( C O ) 12 (9) always lower than those obtained for the for the Rh-Co clusters but selectivities in ethanol are RuCo3 system s precedently described [153, 300]. 16). 16. Homologation of Methanol Catalyzed by Mixed-Metal Clusters3 (adapted from ref. 4 30 41 51 23 1 1 1 . 3 1 . 13 mol), methanol (500 mmol), Mel(5 mmol), CO (40 atm) and H2 (80 atm), 3 hours at 180 °C.
H20(g) + CO(g) ------------------- -- H2(g) + C 0 2 (g) (10) The reaction is extremely slow in the absence of catalyst. It appears that catalysis of the WGSR can be effected by a surprisingly wide range of metal complexes and under markedly different reaction conditions. A result of particular interest is the higher catalytic activity of mixed-metal carbonyl clusters compared to homonuclear metal carbonyls alone. 5). either However, comparable activity was observed with a mixture of Fe(CO)5 and Ru3(C O ) 12 in alkaline solution.
C o o r d in a tiv e ly the active in the by Recent O jim a e v id e n c e u n s a t u r a te d species [220b]. hydroformylation step [2 2 0 a ] points b im e t a llic in the to the co m p o u n d Excellent regioselectivities of the hydroformylation- amidocarbonylation of trifluoropropene (eq. 13) using a C o 2 ( C O ) 8/ R h 6 ( C O ) 16 system in which 62 could be generated as well. 00H H 3C v + F3C A mixed-metal ^ 'N H C O C H g CoxR h y ( C O ) z species COOH ) -------- < f 3c has (13) NHCOCH3 also been postulated previously as an active catalyst in the hydrocarbonylation of diketene .
Chemical Bonds–Better Ways to Make Them and Break Them by Ivan Bernal (Eds.)