Abstract
The reaction of α-clopropylstyrene (CPS) with HMn(CO)5 can result in either hydrogenation or hydroformylation. The hydrogenation occurs by a previously established pathway involving sequential hydrogen atom transfers from the metal hydride to the organic substrate, and is the predominant reaction observed with samples of HMn(CO)5 that have been thoroughly dried and purified using P2O5. With samples of HMn(CO)5 that have been not been treated with P2O5, the reaction that occurs with CPS is ring-opening hydroformylation, leading to the isolation of Mn2(CO)9(η1-HCOCH2CH2CHC(Ph)CH3). The detailed procedures for preparation and handling of HMn(CO)5 that are reported in this paper enable the hydroformylation reaction to be reproducible observed as the predominant reaction. An induction period of a few hours is typically observed in the hydroformylation, but addition of Mn2(CO)9(η1-tolualdehyde) eliminates the induction period. The hydroformylation reaction is inhibited by CO (1 atm). The manganese alkyl complex (CO)5MnCH2CH2CHC(Ph)CH3 is an intermediate in the hydroformylation. The details of the mechanism of formation of this alkyl complex from CPS and HMn(CO)s are not completely understood, but several mechanistic possibilities are considered.
| Original language | English |
|---|---|
| Pages (from-to) | 345-368 |
| Number of pages | 24 |
| Journal | Journal of Organometallic Chemistry |
| Volume | 429 |
| Issue number | 3 |
| DOIs | |
| Publication status | Published - May 26 1992 |
Fingerprint
ASJC Scopus subject areas
- Biochemistry
- Chemical Engineering (miscellaneous)
- Inorganic Chemistry
- Organic Chemistry
- Physical and Theoretical Chemistry
- Materials Science (miscellaneous)
- Materials Chemistry
Cite this
Formation of a manganese alkyl complex as an intermediate in the ring-opening hydroformylation of α-cyclopropylstyrene by HMn(CO)5 . / Bullock, R Morris; Rappoli, Brian J.
In: Journal of Organometallic Chemistry, Vol. 429, No. 3, 26.05.1992, p. 345-368.Research output: Contribution to journal › Article
}
TY - JOUR
T1 - Formation of a manganese alkyl complex as an intermediate in the ring-opening hydroformylation of α-cyclopropylstyrene by HMn(CO)5
AU - Bullock, R Morris
AU - Rappoli, Brian J.
PY - 1992/5/26
Y1 - 1992/5/26
N2 - The reaction of α-clopropylstyrene (CPS) with HMn(CO)5 can result in either hydrogenation or hydroformylation. The hydrogenation occurs by a previously established pathway involving sequential hydrogen atom transfers from the metal hydride to the organic substrate, and is the predominant reaction observed with samples of HMn(CO)5 that have been thoroughly dried and purified using P2O5. With samples of HMn(CO)5 that have been not been treated with P2O5, the reaction that occurs with CPS is ring-opening hydroformylation, leading to the isolation of Mn2(CO)9(η1-HCOCH2CH2CHC(Ph)CH3). The detailed procedures for preparation and handling of HMn(CO)5 that are reported in this paper enable the hydroformylation reaction to be reproducible observed as the predominant reaction. An induction period of a few hours is typically observed in the hydroformylation, but addition of Mn2(CO)9(η1-tolualdehyde) eliminates the induction period. The hydroformylation reaction is inhibited by CO (1 atm). The manganese alkyl complex (CO)5MnCH2CH2CHC(Ph)CH3 is an intermediate in the hydroformylation. The details of the mechanism of formation of this alkyl complex from CPS and HMn(CO)s are not completely understood, but several mechanistic possibilities are considered.
AB - The reaction of α-clopropylstyrene (CPS) with HMn(CO)5 can result in either hydrogenation or hydroformylation. The hydrogenation occurs by a previously established pathway involving sequential hydrogen atom transfers from the metal hydride to the organic substrate, and is the predominant reaction observed with samples of HMn(CO)5 that have been thoroughly dried and purified using P2O5. With samples of HMn(CO)5 that have been not been treated with P2O5, the reaction that occurs with CPS is ring-opening hydroformylation, leading to the isolation of Mn2(CO)9(η1-HCOCH2CH2CHC(Ph)CH3). The detailed procedures for preparation and handling of HMn(CO)5 that are reported in this paper enable the hydroformylation reaction to be reproducible observed as the predominant reaction. An induction period of a few hours is typically observed in the hydroformylation, but addition of Mn2(CO)9(η1-tolualdehyde) eliminates the induction period. The hydroformylation reaction is inhibited by CO (1 atm). The manganese alkyl complex (CO)5MnCH2CH2CHC(Ph)CH3 is an intermediate in the hydroformylation. The details of the mechanism of formation of this alkyl complex from CPS and HMn(CO)s are not completely understood, but several mechanistic possibilities are considered.
UR - http://www.scopus.com/inward/record.url?scp=0011477951&partnerID=8YFLogxK
UR - http://www.scopus.com/inward/citedby.url?scp=0011477951&partnerID=8YFLogxK
U2 - 10.1016/0022-328X(92)83184-J
DO - 10.1016/0022-328X(92)83184-J
M3 - Article
AN - SCOPUS:0011477951
VL - 429
SP - 345
EP - 368
JO - Journal of Organometallic Chemistry
JF - Journal of Organometallic Chemistry
SN - 0022-328X
IS - 3
ER -