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14. 41 42 hydroformylation catalysts at 95 °C. In contrast, cobalt-containing clusters, such as the triangular Co2P t(D P P E )(C O )7 (26), the linear Co2Pt(CO)gL2 (L = c -C 6H 11NC) (23a) and the tetranuclear Co2P t2( C O ) 8(P P h 3)2 (28a) were quite active catalysts within the 80-100 °C range but not at 60-65 °C. A remarkable ligand effect was noticed when comparing the catalytic activity of 26 vs. that of its isostructural analogue Co2 P t( D P A E ) ( C O ) 8 (27). The former was an active hydroformylation catalyst at 80 °C whereas the DPAEligated 27 was inert.

Monovalent metal salts having general formula M2[ R h 12(C O )30], where M is Cu (4 1 a ), Ag (4 1 b ), Au (4 1 c ) or Ir (41 d) have also been evaluated as catalyst precursors in the reaction of CO and H2 to produce oxygenated compounds such as methanol, ethylene propylene glycol. recrystallization The [310a]. clusters were recovered glycol, glycerol and 1,2from the filtrate by Similarly, divalent metal salts of general formula M '[R h 12(C O )30] where M' is Mn (42a), Co (42b), Zn (42c) or Pt (42d) as well as trivalent metal salts of the type M"2[R h 12(C O )30]3 in which M" is Ir (43a) or Re (43b) catalyze the synthesis of organic compounds from CO and H2 [310b, 310c].

307]). Fe Ru Os Co Rh Ir a b c Fe Ru Os Co Rh Ir 5 250 15 0 c 0 0 36 c 0 30 140 c 700 590 32 24a 3b 1 130 3 Activity of a mixture of RuClß and [lr(CO>3Cl2]2 as a catalyst precursor. Activity of a mixture of Os3 ( C O ) i 2 + [lr(CO)3 Cl 2 ]2 Not studied. 32 2. 4. HYDROFORMYLATION REACTIONS The mixed-metal complex Cp2Zr(C H 2PPh2)2RhH (PPh3) (57) was found to be an active hydroformylation catalyst at 80 °C and 20 atm (H2/CO = 1 : 1). A high rate of conversion of 1-hexene was observed, branched selectivity decreased during the course of the but the normal/ reaction to reach a ratio of ca.

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