By Ivan Bernal (Eds.)
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Additional info for Chemical Bonds–Better Ways to Make Them and Break Them
5. CARBONYLATION REACTIONS The carbonylation of 1-octene was studied under mild conditions (75°C, 50 atm) using the iron-palladium complex [(OC)4F e P d ^ - P P h 2)CI]2 (30), (eq. 19). CO -------------► CH3(CH2)5CH CH3(CH2)5CH = CH2 + CH3(CH2)7C02Et (19) ^ C02Et 4 % HCI, EtOH Catalyst The total yield of esters was ten times greater for the mixed-metal catalyst than for PdCI2(PPh3)2. The distribution of isomer products is ca. 1 :1, with a tendency for the is o to predominate. Complex 30 was also an effective catalyst for the carbonylation of 1,5-cyclooctadiene (eq.
3 Pentane - - 1 . 2 ? 8 . 9 cis - ? 01 mmol of catalyst were used. 6 W 2 P d 2 ( C O ) 6 C p 2l-2 1 7 Pd 2 (CO)6 C p 2 l- 2 M 02 P d 2 (C O )e C p 2 L 2 1 5 2 M o2Pd2(CO)6Cp2l-2 14 6 Formula N° Catalyst precursor Presence of the Planar, Triangulated Clusters 1 4 - 1 9 a and 26 (from ref. ). 18. in the 51 52 All these clusters were found to be suitable catalysts for this reaction. 19). Furthermore, after photolysis, the clusters 4a, 6 3 a -c , 66, 83 and 84 could be recovered (90-98 %) by chromatography on neutral silica gel [233a].
17. Relative Rates for the Dimerization of Norbornadiene to "Binor-S " (T = 46 °C) (from ref. ). 18 stereospecific dimerization of NBD to "Binor-S" was also obtained with catalysts having a Co2Pt (23) or a Fe2Pt (24) linear framework, a butterfly Cluster L L 23a 23 b 24a 24 b 25a 25 b 80a 80 b 81a 81b core, as M Co Co Fe Fe Mo Mo W W Mn Mn in Co2Pt2(C O )8L2 (L = L c-C gH iiN C f-BuNC c-CßH-iiNC f-BuNC c-CgH-dNC f-BuNC c-C eH ^N C f-BuNC c-C gH ^N C f-BuNC X CO CO NO NO Cp Cp Cp Cp (CO)2 (CO)2 49 P P h 3 , 2 8 a ; L = PEt3 , 2 8 b ) Pt3C o2(CO )9 L3 (82), or a trigonal bipyramidal structure, as in in the presence of a Lewis acid .