article · Organometallics
Organometallic migratory insertion reactions can proceed efficiently without any liquid solvent, taking place directly between solid reactants. Testing involved molybdenum, tungsten, and iron carbonyl methyl complexes reacting with triphenylphosphine and various other phosphorus and arsenic ligands at temperatures ranging between 40 and 90 degrees Celsius. These reactions yielded the corresponding acyl and alkyl complexes in moderate to excellent yields reaching up to 100 per cent. Solid-state decarbonylation was also observed at 120 degrees Celsius. Kinetic measurements showed that the solid-state reaction rate between the molybdenum complex and triphenylphosphine is comparable to rates previously recorded in toluene solution under similar conditions. The processes displayed pseudo-first-order behaviour, with diffusion effects influencing the reaction rate at lower temperatures and lower ligand concentrations.
Industrial chemical synthesis often relies on organic solvents, which can create significant safety, environmental, and disposal challenges. Showing that organometallic transformations can proceed directly between solid reagents, at speeds comparable to standard solution-phase processes, suggests routes towards cleaner, solvent-free chemical manufacturing methods.
This work represents early-stage fundamental research into solvent-free synthesis of organometallic compounds. While eliminating organic solvents is relevant to chemical manufacturers and synthetic chemists looking to reduce waste, the abstract focuses entirely on reaction kinetics and small-scale laboratory trials. The research does not detail a specific product, scale-up process, or commercial application pathway.
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Migratory insertion reactions of organometallic complexes have been shown to occur in the absence of solvent and, more significantly, between solid reagents. Reaction between (η 5 -C 5 H 5 )M(CO) 3 Me (M = Mo, W) or (η 5 -C 5 H 5 )Fe(CO) 2 Me and PPh 3 (no solvent) took place at temperatures between 40 and 90 °C and gave the products (η 5 -C 5 H 5 )M(CO) 2 (PPh 3 )COMe and (η 5 -C 5 H 5 )Fe(CO)(PPh 3 )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 (η 5 -C 5 H 5 )Mo(CO) 2 (PPh 3 )COMe to yield (η 5 -C 5 H 5 )Mo(CO) 2 (PPh 3 )Me also occurred in the solid state (120 °C). Reaction of (η 5 -C 5 H 5 )Mo(CO) 3 Me with a range of ligands, L (L = PPh 3, P( p -MeOC 6 H 4 ) 3, PCy 3, PEt 3, AsPh 3, POPh 3, P(OEt) 3; 1:1 reagent ratio, 90 °C, 15 min), in the absence of solvent gave (η 5 -C 5 H 5 )Mo(CO) 2 (L)COMe (7−100% yield) and, on extended reaction, (η 5 -C 5 H 5 )Mo(CO) 2 (L)Me in varying yields. A kinetic study of the solid-state reaction between (η 5 -C 5 H 5 )Mo(CO) 3 Me and PPh 3 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 PPh 3 . Diffusional effects on the reaction rate are detected at low temperature and low PPh 3 ratios.
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DOI: 10.1021/om0301738
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