By Ivan Bernal (Eds.)
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This mixture is unexpectedly superior to the anticipated additive effects of the individual metal complexes. This reaction is also temperature dependent [99, 100b]. Improved catalytic activities have been observed with the mixed clusters HRuCo3(CO) 12 (53) and M[RuCo3(C O )12] (69a-e) promoted by methyl iodide, compared with those for Co2(C O )8 or Ru3(C O ) 12 alone [99, 151-153, 300]. The yield of ethanol depends upon the nature of the cation employed [152], Another Ru-Co mixed cluster, 70a, gave lower yield of ethanol under the same conditions [152, 153], Although consistent transformations (eq.
The complexes 58a and 58b could be recovered after catalysis [276, 277]. t-B u t-B u (O C )R h R h (C O ) / \ P h 9P 58a , X = Zr(Cp)2 PPh n 58b , X = A synergic effect [Et4N ][F e C o3(C O )12] was observed when -C H 2-C H 2- the mixed-metal cluster (59b) was used as catalyst in the hydroformylation of cyclohexene to yield cyclohexanecarbaldehyde (CHC) (eq. 9). In com parison, structure, [Et4 N ] [ F e 3C o ( C O ) 13] (60 b), which exhibited has also a tetrahedral little activity. Addition of Fe3 ( C O ) 12, with or without 33 [B u 4 N]CI, to C o 2 ( C O ) 8 did not improve the activity [150].
D Ru, 6 x 10"4 g. atom. e T = 130 °C. f Benzene as solvent, 10 mL. 9, a similar synergic effect was (53) w as assembling investigated in also the observed. pre s en c e The of activity of H R u C o 3 ( C O ) 12 tr iphenylphosphine ligand tris(d iphenylphosphino)m ethane, or of the expected to maintain the metals in close proximity. The results were similar to those obtained for the F e C o 3 cluster 5 9 b . in creasing the R u /C o H o w e v e r, ratio the [1 5 0 , activity 1 51 ]. w as The greatly improved h ydrofo rm ylatio n by when the 34 bimetallic catalysts was remarkably influenced by the nature of the solvent used, and alcohols such as methanol and ethanol were the best among the solvents employed [151].