Molybdenum complexes acrylonitrile

Molybdenum, tris(phenylenedithio)-structure, 1,63 Molybdenum alkoxides physical properties, 2,346 synthesis, 2,339 Molybdenum blue liquid-liquid extraction, 1,548 Molybdenum cofactor, 6,657 Molybdenum complexes acrylonitrile, 2,263 alkoxides, 3,1307 alkoxy carbonyl reactions, 2,355 alkyl, 3,1307 alkyl alkoxy reactions, 2,358 alkyl peroxides oxidation catalyses, 6,342 allyl, 3,1306... 

Acrylonitrile seems to be a rather versatile ligand. As shown on p. 21 it may bond as a 77-ethylenic ligand. With molybdenum and tungsten, however, it forms complexes in which it bonds to fte metal by the nitrile group, e.g. CH2=CHCNMo(CO)s [88, 89] and thus behaves like CH3CN. It can also form the polymeric complex (acrylonitrile)2Mo(CO)2 [90], which may have a stmcture related to that proposed for the acrolein complex, 3.34. 

MAA and MMA may also be prepared via the ammoxidation of isobutylene to give meth acrylonitrile as the key intermediate. A mixture of isobutjiene, ammonia, and air are passed over a complex mixed metal oxide catalyst at elevated temperatures to give a 70—80% yield of methacrylonitrile. Suitable catalysts often include mixtures of molybdenum, bismuth, iron, and antimony, in addition to a noble metal (131—133). The meth acrylonitrile formed may then be hydrolyzed to methacrjiamide by treatment with one equivalent of sulfuric acid. The methacrjiamide can be esterified to MMA or hydrolyzed to MAA under conditions similar to those employed in the ACH process. The relatively modest yields obtainable in the ammoxidation reaction and the generation of a considerable acid waste stream combine to make this process economically less desirable than the ACH or C-4 oxidation to methacrolein processes. 

A number of transition metal complexes have been apphed in ATRP process. It has been successful for molybdenum, chromium, rhenium, ruthenium, and iron, rhodiiun, nickel, palladium, and copper complexes. Among these, copper catalysts are superior in terms of versatihty and cost. Styrenes, (meth)acrylates, (meth)acrylamides, and acrylonitrile have been successfully polymerized using copper-mediated ATRP. The polymerization has been foimd to be tolerant to a variety of... 

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