Solvent-Free Organometallic Migratory Insertion Reactions
| dc.contributor.author | Adeyemi, Olalere | |
| dc.date.accessioned | 2022-02-08T09:50:02Z | |
| dc.date.available | 2022-02-08T09:50:02Z | |
| dc.date.issued | 2003-03-10 | |
| dc.description.abstract | Migratory insertion reactions of organometallic complexes have been shown to occur in the absence of solvent and, more significantly, between solid reagents. Reaction between (η5-C5H5)M(CO)3Me (M ) Mo, W) or (η5-C5H5)Fe(CO)2Me and PPh3 (no solvent) took place at temperatures between 40 and 90 °C and gave the products (η5-C5H5)M(CO)2(PPh3)COMe and (η5-C5H5)Fe(CO)(PPh3)COMe in moderate to good yield (60-99%). The Mo and W complexes reacted in the solid state when T < 80 °C. The decarbonylation of (η5-C5H5)- Mo(CO)2(PPh3)COMe to yield (η5-C5H5)Mo(CO)2(PPh3)Me also occurred in the solid state (120 °C). Reaction of (η5-C5H5)Mo(CO)3Me with a range of ligands, L (L ) PPh3, P(p MeOC6H4)3, PCy3, PEt3, AsPh3, POPh3, P(OEt)3; 1:1 reagent ratio, 90 °C, 15 min), in the absence of solvent gave (η5-C5H5)Mo(CO)2(L)COMe (7-100% yield) and, on extended reaction, (η5-C5H5)Mo(CO)2(L)Me in varying yields. A kinetic study of the solid-state reaction between (η5-C5H5)Mo(CO)3Me and PPh3 yielded rate constants, e.g. k ) 5.18 × 10-5 s-1 (Mo:P ) 1:10; 50 °C), which compares with the literature solution data in toluene (k ) (0.8-2.5) × 10-5 s-1, 50 °C) using similar metal to ligand ratios. The data are consistent with a pseudo-first order reaction in the presence of PPh3. Diffusional effects on the reaction rate are detected at low temperature and low PPh3 ratios | en_US |
| dc.identifier.uri | http://dspace.run.edu.ng:8080/jspui/handle/123456789/1062 | |
| dc.language.iso | en | en_US |
| dc.title | Solvent-Free Organometallic Migratory Insertion Reactions | en_US |
| dc.type | Article | en_US |