Maria B. Ezhova, Brian R. James (auth.), László I. Simándi's Advances in Catalytic Activation of Dioxygen by Metal PDF

By Maria B. Ezhova, Brian R. James (auth.), László I. Simándi (eds.)

ISBN-10: 0306478161

ISBN-13: 9780306478161

ISBN-10: 1402010745

ISBN-13: 9781402010743

The topic of dioxygen activation and homogeneous catalytic oxidation by means of steel complexes has been within the concentration of cognizance over the past two decades. The frequent curiosity is illustrated through its routine presence one of the periods and topic parts of significant foreign meetings on numerous facets of bioinorganic and coordination chemistry in addition to catalysis. the main trendy examples are ICCC, ICBIC, EUROBIC, ISHC, and naturally the ADHOC sequence of conferences concentrating on the topic itself. equally, the variety of unique and evaluation papers dedicated to quite a few features of dioxygen activation are at the upward thrust. This pattern is due evidently to the relevance of catalytic oxidation to organic procedures resembling dioxygen delivery, and the motion of oxygenase and oxidase enzymes on the topic of metabolism. The structural and practical modeling of metalloenzymes, quite of these containing iron and copper, by way of low-molecular complexes of iron, copper, ruthenium, cobalt, manganese, etc., have supplied a wealth of oblique details aiding to appreciate how the energetic facilities of metalloenzymes might function. the data received from the examine of metalloenzyme types is additionally acceptable within the layout of transition steel complexes as catalytsts for particular reactions. This method has become referred to as biomimetic or bioinspired catalysis and remains to be a fruitful and increasing sector of research.

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In contrast, with the M-41(m) system, the polymer oxidized trans-stilbene and to the corresponding trans epoxides in 90 and 86 % yields, respectively. Several alkenes were oxidized catalytically for the first time with high selectivity: 3,4-dihydronaphthalene yielded 62% epoxide, 38 Maria B. Ezhova and Brian R. James 1,5-cyclooctadiene gave only bis-epoxide (76%), and cis-1-phenyl-3-penten1-yne only gave cis-epoxide (91%). The 3,4,6-tri-O-acetyl-D-glucal was epoxidized to only (56%), while the system gave a 3 : 1 mixture of and (see Fig.

The highly distorted (X-Ray data revealed that its precursor, Ru(DPP)(CO)(py), also exhibits both saddle and ruffle distortion)123 catalyzes in benzene-MeCN (9:1) some epoxidation of norbornene, styrene, cyclohexene, cyclooctene and cis-stilbene under 1 atm with turnovers of 8 - 40 in 4 h before deactivation of catalyst123; the numbers are comparable with those for and greater than for and There were also co-oxidation products: benzaldehyde (7 turnovers) and trace phenylacetylaldehyde were formed from styrene, cyclohex-2-en-1-ol (20 turnovers) and cyclohex-2-en-1-one (11 turnovers) from cyclohexene, and trace benzaldehyde and trans-stilbene 28 Maria B.

The initial cycle starts with slow oxidation of the olefin by to give and epoxide (step a), the monooxo complex then reacting rapidly with N-oxide to form complex (15) (step b). (15) is then considered to effect very rapid epoxidation with liberation of the pyridine (step c). Regeneration of from (15) (step d) was ruled out, as this step was slower than epoxidation via (15). The role of coordinated pyNO was rationalized in terms of its effect on the chiral environment on the trans oxo-coordination site137.

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Advances in Catalytic Activation of Dioxygen by Metal Complexes by Maria B. Ezhova, Brian R. James (auth.), László I. Simándi (eds.)


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