Abstract
2-Phenyl-1-methylenecyclopropane is isomerized into 2-phenyl-1,3-butadiene and 1-phenyl-1,3-butadiene in the presence of catalytic amounts of RhH(CO)(PPh3)3 and RhH(PPh3)4. The Rh-containing product of the reactions has a 2-phenyl-1-methylallyl (or 1-phenyl-1-methylallyl) ligand, and is formed also from the reaction of 2-phenyl-1,3-butadiene with RhH(CO)(PPh3)3. RhH(CO)(PPh3)3 promotes ring-opening isomerization of 4-phenyl-1-methylenespiro[2,2]pentane to afford Rh[η3-anti- CH2C{C(CH2)Ph}CHCH3](PPh3) 2 (2) at 50 °C and Rh{κ1,η2- CH2CH(Ph)C(CH2)CHCH2}(CO)(PPh3) 2 (3) at -35°C. X-ray crystallography of 2 shows the π-allylic ligand having a methyl group at anti position. The mechanism for formation of 2 via intermediate 3 is discussed.
Original language | English |
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Pages (from-to) | 65-71 |
Number of pages | 7 |
Journal | Journal of Molecular Catalysis A: Chemical |
Volume | 241 |
Issue number | 1-2 |
DOIs | |
Publication status | Published - Nov 1 2005 |
Externally published | Yes |
Keywords
- CC bond activation
- Diene
- Hydrido complex
- Methylenecyclopropane
- Rhodium
ASJC Scopus subject areas
- Catalysis
- Process Chemistry and Technology
- Physical and Theoretical Chemistry