9 resultados para IRIDIUM 192
em Brock University, Canada
Resumo:
N-heterocyclic carbenes (NHCs) have undergone rapid development in recent years. Due to their strong a-electron donation and structural variability properties, NHCs are becoming a major class of ligands in organometallic chemistry. Compared with the other two types of NHCs (imidazolylidenes and imidazolinylidenes), benzimidazolylidenes have not been well represented. Limited synthetic approaches may impede the development ofbenzimidazolylidenes. This thesis is focused on the synthesis of phenanthroline-derived benzimidazolylidene ligands and their metal complexes. A series of benzimidazolylidene-iridium complexes were synthesized and characterized spectroscopically and crystallographic ally. All of the new complexes showed varying degrees of catalytic activity and enantioselectivity toward transfer hydrogenation and asymmetric hydrogenation. The best results were achieved in hydrogenation of methyl-2-acetamidoacrylate, which afforded (-)-(R)-methyl-2-acetamidopropanoate in 97% yield and 81 % ee.
Resumo:
Iridium complexes with bidentate P,N ligands represent a class of catalysts that significantly expand the application range of asymmetric hydrogenation. New substrate classes, for which there have previously been no suitable catalysts, can now be efficiently hydrogenated in high conversion and enantioselectivity. These substrates are often of synthetic importance, thus iridium catalysis represents a significant advance in the field of asymmetric catalysis. Planar chiral ferrocenyl aminophosphine ligands in which both heteroatoms were directly bound to the cyclopentadienyl ring were prepared by BF3-activated lithiationsubstitution in the presence of a chiral diamine in 49-59% yield and 75-85% enantiomeric excess. Some of these ligands were recrystallized to enantiomeric purity via ammonium fluoroborate salt formation of the phosphine sulfide. A crystal structure of one of these compounds was obtained and features an intramolecular hydrogen bond between the nitrogen, hydrogen, and sulfur atoms. Neutralization, followed by desulfurization, provided the free ligands in enantiomeric purity. Iridium complexes with these ligands were formed via reaction with [Ir(COD)Clh followed by anion exchange with NaBArF. These complexes were successfully applied in homogeneous hydrogenation of several prochiral substrates, providing products in up to 92% enantiomeric excess. Variation of the dimethyl amino group to a pyrrolidine group had a negative effect on the selectivity of hydrogenation. Variation of the substituents on phosphorus to bulkier ortho-tolyl groups had a positive effect, while variation to the more electron rich dicyclohexyl phosphine had a negative effect on selectivity.
Resumo:
License no. 144 of season 1872/73 made out to S.D. Woodruff for 36 square miles in berth no. 192. This document is slightly torn and stained along the right hand side. This does not affect the text, April 7, 1873.
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License no. 67 of season 1873/74 made out to S.D. Woodruff for 36 square miles in berth no. 192, June 13, 1873
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License no. 5 of season 1875/76 made out to S.D. Woodruff for 36 square miles in berth no. 192, June 1, 1875.
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License no. 2 of season 1886/87 made out to S.D. Woodruff for 36 square miles in berth no. 192, May 15, 1876.
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License no. 6 of season 1877/78 made out to S.D. Woodruff for 36 square miles in berth no.192, May 31, 1877.
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License no. 87 of season 1879/80 made out to S.D. Woodruff for 36 square miles in berth no. 192, June 3, 1879.
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License no. 26 of season 1880/81 made out to S.D. Woodruff for 36 square miles in berth no. 192, May 27, 1880.
