作者: Cornelius G. Kreiter , Klaus Lehr , Michael Leyendecker , William S. Sheldrick , Reiner Exner
关键词: Aliphatic compound 、 Molecule 、 Medicinal chemistry 、 Chemistry 、 Stereochemistry 、 Conjugated system 、 Manganese 、 Transition metal 、 Double bond 、 Cycloaddition 、 Side reaction
摘要: Photochemical Reactions of Transition Metal Organyl Complexes with Olefines, 31). – [4 + 5] Cycloaddition Conjugated Dienes to Tricarbonyl(η5-2,4-dimethyl-2,4-pentadienyl)manganese Tricarbonyl(η5-2,4-dimethyl-2,4-pentadienyl)manganese [1] reacts photochemically the acyclic conjugated dienes 1,3-butadiene [A], 2-methyl-1,3-butadiene [B], (E)-1,3-pentadiene (C), (E,E)-2,4-hexadiene (D), 2,4-dimethyl-1,3-pentadiene (E), 2,4-hexadien-1-ol (F), and methyl 2,4-hexadienoate (G) in a formal cycloaddition give tricarbonylmanganese complexes η3:2-2,6-cyclononadien-1-yl ligands (2A-2G). In addition, reaction 1 A yields thermolabile [η3:2:2-1-(3-butene-1,2-diyl)-1,3-dimethyl-2,6-cyclononadiene]dicarbonylmanganese (3A) E,E E,Z isomers [η3-1-(2-butene-1,1-diyl)-1,3-dimethyl-2,6-cyclononadiene]tetracarbonylmanganese (4A, 4A] as byproducts. Similarly, B form tetracarbonyl[η3-1-(3-methyl-2-butene-1,1-diyl)-1,3,6-trimethyl1-2,6-cyclononadiene]manganese (4B) side reaction. The crystal molecular structures tricarbonyl(η3:2-1,3,5,5,7-pentamethyl-2,6-cyclononadien-1-yl]manganese (2E) 3A are determined by X-ray structure analyses. each formally octahedral unusual long manganese–carbon bonds found for one coordinated CC double bond hydrocarbon ligands.