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Trapping the dirhenium alkynyl Fischer type carbene through Michael addition. Unexpected room-temperature E/Z isomerization of (CO)5Re(CO)4Re(=C(OMe)CH=C(NMe2)TMS.
Autorzy
Rok wydania
2006
Czasopismo
Numer woluminu
25
Strony
3544-3547
DOI
10.1021/om0510977
Kolekcja
Język
Angielski
Typ publikacji
Artykuł
The reaction of Re-2(CO)(10) with LiC CTMS and Me3O+BF4- results in a low-stability Fischer type alkynyl carbene complex, (CO)(5)Re(CO)(4)Re(=C(OMe)C CTMS). This easily reacts with HNMe2 to give the stable ( CO) 5Re( CO) 4Re( (=C(OMe)CH=C(NMe2)TMS) in 82% yield, which exhibits unrestrained rotation around the carbon-carbon "double bond", resulting in room-temperature E/Z isomerization. The aminolysis product (CO)(5)Re(CO)(4)Re(=C(NMe2)C CTMS) was also generated from (CO)(5)Re(CO)(4)Re(=C(OMe)C CTMS) and could be desilylated to form the acetylene carbene (CO)(5)Re(CO)(4)Re(=C(NMe2)C CH).
Adres publiczny
https://doi.org/10.1021/om0510977