35795-61-0Relevant academic research and scientific papers
Solvent-free organometallic migratory insertion reactions
Adeyemi, Olalere G.,Coville, Neil J.
, p. 2284 - 2290 (2003)
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)2 Me 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 5-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. κ = 5.18 × 10-5 s-1 (Mo:P = 1:10; 50°C), which compares with the literature solution data in toluene (κ = (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.
