By Ivan Bernal (Eds.)
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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.
Asymmetric hydrosilation with the optically active cluster (+)-84 would provide irrefutable evidence for involvement of the intact chiral SMoFeCo tetrahedron during catalysis. 19 (X = 355 nm), B (48 %), racemic A (16 %) and racemic cluster 84 were isolated after 12 days. It has been subsequently established that the photoracemization of (+)-84 at X = 355 nm proceeds substantially faster than the hydrosilation reaction [233a]. 53 2. 10. CONCLUSION In this Section, we have examined the various reactions in which m ixed-m etal cluster com pounds have been used as precursors of homogeneous catalysts.
On the other hand, 76 and C d [ C o (C O )4]2 (77), mixtures of dim ers, including "Binor-S", under the same conditions. of gave The mercury a nalogue H g [C o (C O )4]2 (78) dimerizes norbornadiene to a mixture of four dim ers but no "Binor-S" is formed. In the presence of Lewis acids, however, this catalyst gives "Binor-S" exclusively . It was also found that C o 2 [ Z n C o ( C O ) 4] 2 ( C O ) 7 (79) catalyst for the ste reospecific dim erization is an efficient of n o rb ornad ien e. The main difference observed when comparing 79 with Z n [C o (C O )4]2 (76) was that the induction 79 .