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Photolysis of Tricarbonyl(η 5 ‐cyclohexadienyl)manganese in Tetrahydrofuran, Reactions with Cumulated Dienes
Author(s) -
Kreiter Cornelius G.,
Wachter Norbert K.,
Reiß Guido J.
Publication year - 1999
Publication title -
european journal of inorganic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.667
H-Index - 136
eISSN - 1099-0682
pISSN - 1434-1948
DOI - 10.1002/(sici)1099-0682(199904)1999:4<655::aid-ejic655>3.0.co;2-y
Subject(s) - chemistry , adduct , tetrahydrofuran , photodissociation , manganese , solvent , mass spectrometry , medicinal chemistry , nuclear magnetic resonance spectroscopy , reactive intermediate , spectroscopy , crystal structure , infrared spectroscopy , stereochemistry , photochemistry , crystallography , catalysis , organic chemistry , physics , chromatography , quantum mechanics
[Mn(η 5 ‐C 6 H 7 )(CO) 3 ] ( 1 ) forms highly reactive [Mn(η 5 ‐C 6 H 7 )(CO) 2 (THF)] ( 2 ) upon UV irradiation in THF at 208 K. Solvent complex 2 reacts between 208 and 293 K with 1,1‐disubstituted allenes C 3 H 2 RR′ [R, R′ = CH 3 , CH 3 ( A ); CH 3 , C 6 H 5 ( B ); C 2 H 5 , C 6 H 5 ( C ); C 6 H 5 , C 6 H 5 ( D ); OCH 3 , Si(CH 3 ) 3 ( E )] to four different types of complexes: The [5+2] cycloadduct [Mn(η 3:2 ‐C 9 H 9 RR′)(CO) 3 ] ( 3E ), rearranged [5+2] cycloadducts [Mn(η 3:2 ‐C 9 H 9 RR′)(CO) 3 ] ( 4B , 4C , 4D ), 1:2 adducts [Mn(η 3:2 ‐C 12 H 11 R 2 R′ 2 )(CO) 3 ] ( 5A – 5E ), and the 1:3 adduct [Mn{η 3:2:2 ‐C 15 H 13 (CH 3 ) 6 }(CO) 2 ] ( 6A ). The constitutions of the products were established by IR and NMR spectroscopy, as well as by C,H elemental analysis and mass spectrometry. The crystal and molecular structure of 6A was determined by X‐ray structure analysis. A formation mechanism for the complexes is proposed.