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 |
|---|---|
| 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 |
Fingerprint
Keywords
- CC bond activation
- Diene
- Hydrido complex
- Methylenecyclopropane
- Rhodium
ASJC Scopus subject areas
- Catalysis
- Process Chemistry and Technology
- Materials Science (miscellaneous)
Cite this
Ring-opening isomerization of methylenecyclopropanes catalyzed by hydridorhodium(I) complexes. / Itazaki, Masumi; Nishihara, Yasushi; Takimoto, Hisami; Yoda, Chikako; Osakada, Kohtaro.
In: Journal of Molecular Catalysis A: Chemical, Vol. 241, No. 1-2, 01.11.2005, p. 65-71.Research output: Contribution to journal › Article
}
TY - JOUR
T1 - Ring-opening isomerization of methylenecyclopropanes catalyzed by hydridorhodium(I) complexes
AU - Itazaki, Masumi
AU - Nishihara, Yasushi
AU - Takimoto, Hisami
AU - Yoda, Chikako
AU - Osakada, Kohtaro
PY - 2005/11/1
Y1 - 2005/11/1
N2 - 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.
AB - 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.
KW - CC bond activation
KW - Diene
KW - Hydrido complex
KW - Methylenecyclopropane
KW - Rhodium
UR - http://www.scopus.com/inward/record.url?scp=25844524691&partnerID=8YFLogxK
UR - http://www.scopus.com/inward/citedby.url?scp=25844524691&partnerID=8YFLogxK
U2 - 10.1016/j.molcata.2005.06.045
DO - 10.1016/j.molcata.2005.06.045
M3 - Article
AN - SCOPUS:25844524691
VL - 241
SP - 65
EP - 71
JO - Journal of Molecular Catalysis A: Chemical
JF - Journal of Molecular Catalysis A: Chemical
SN - 1381-1169
IS - 1-2
ER -