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Photochemische Reaktionen von Übergangsmetall‐Organyl‐Komplexen mit Olefinen, 3. [4 + 5]‐Cycloaddition konjugierter Diene an Tricarbonyl(η 5 ‐2,4‐dimethyl‐2,4‐pentadienyl)mangan
Author(s) -
Kreiter Cornelius G.,
Lehr Klaus,
Leyendecker Michael,
Sheldrick William S.,
Exner Reiner
Publication year - 1991
Publication title -
chemische berichte
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.667
H-Index - 136
eISSN - 1099-0682
pISSN - 0009-2940
DOI - 10.1002/cber.19911240102
Subject(s) - chemistry , cycloaddition , manganese , medicinal chemistry , double bond , dimethyl acetylenedicarboxylate , conjugated system , crystal structure , carbyne , stereochemistry , carbene , polymer chemistry , catalysis , organic chemistry , polymer
Photochemical Reactions of Transition Metal Organyl Complexes with Olefines, 3 1) . – [4 + 5] Cycloaddition of Conjugated Dienes to Tricarbonyl(η 5 ‐2,4‐dimethyl‐2,4‐pentadienyl)manganese Tricarbonyl(η 5 ‐2,4‐dimethyl‐2,4‐pentadienyl)manganese [ 1 ] reacts photochemically with 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 [4 + 5] cycloaddition to give tricarbonylmanganese complexes with η 3:2 ‐2,6‐cyclononadien‐1‐yl ligands ( 2A ‐ 2G ). In addition, the reaction of 1 with A yields thermolabile [η 3:2:2 ‐1‐(3‐butene‐1,2‐diyl)‐1,3‐dimethyl‐2,6‐cyclononadiene]dicarbonylmanganese ( 3A ) and E,E and E,Z isomers of [η 3 ‐1‐(2‐butene‐1,1‐diyl)‐1,3‐dimethyl‐2,6‐cyclononadiene]tetracarbonylmanganese ( 4A, 4A ] as byproducts. Similarly, 1 reacts with B to form tetracarbonyl[η 3 ‐1‐(3‐methyl‐2‐butene‐1,1‐diyl)‐1,3,6‐trimethyl1‐2,6‐cyclononadiene]manganese ( 4B ) in a side reaction. The crystal and molecular structures of tricarbonyl(η 3:2 ‐1,3,5,5,7‐pentamethyl‐2,6‐cyclononadien‐1‐yl]manganese (2E) and of 3A are determined by X‐ray structure analyses. In each of the formally octahedral complexes unusual long manganese–carbon bonds are found for one coordinated CC double bond of the hydrocarbon ligands.