Photolysis of Tricarbonyl(η5-cyclohexadienyl)manganese in Tetrahydrofuran, Reactions with Cumulated Dienes

✍ Scribed by Cornelius G. Kreiter; Norbert K. Wachter; Guido J. Reiß

• Publisher: John Wiley and Sons
• Year: 1999
• Tongue: English
• Weight: 299 KB
• Volume: 1999
• Category: Article
• ISSN: 1434-1948
• DOI: 10.1002/(sici)1099-0682(199904)1999:4<655::aid-ejic655>3.0.co;2-y

✦ Synopsis

Mn(η 5 -C 6 H 7 )(CO) 3 ] (1) forms highly reactive [Mn(η 5 -adducts [Mn(η 3:2 -C 12 H 11 R 2 RЈ 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 constitu-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-tions of the products were established by IR and NMR spectroscopy, as well as by C,H elemental analysis and mass disubstituted allenes C 3 H 2 RRЈ [R, RЈ = 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 spectrometry. The crystal and molecular structure of 6A was determined by X-ray structure analysis. A formation (E)] to four different types of complexes: The [5+2] cycloadduct [Mn(η 3:2 -C 9 H 9 RRЈ)(CO) 3 ] (3E), rearranged [5+2] mechanism for the complexes is proposed. cycloadducts [Mn(η 3:2 -C 9 H 9 RRЈ)(CO) 3 ] (4B, 4C, 4D), 1:2