Abstract
The paper presents details of catalytic dehydrogenation reactions of two high molecular weight, highly branched hydrocarbons, a polymer of 1-hexene and an oligomer of 1-butene, and describes kinetic analysis of these reactions. The dehydrogenation reactions were catalyzed with two pincer Ir complexes, [4-methoxy-2,6-C6H3(CH2P-tert-Bu2)2]IrH2 and [4-methoxy-2,6-C6H2(CH2P-iso-Pr2)2]IrH2, and were carried out at 150 °C in p-xylene solutions with norbornene as a hydrogen acceptor. The structure of all dehydrogenation reaction products and the Ir species was determined by 1H and 31P NMR. Mechanistically, these reactions are similar to dehydrogenation reactions of low molecular weight alkanes. Kinetic analysis of the reactions yielded the values of effective rate constants for all major reaction steps in the catalytic cycle. The results show that catalytic dehydrogenation of branched polymers in the presence of an alkene hydrogen acceptor is feasible at increased temperatures and represents a viable route to post-synthetic modification of branched polyolefins.
| Original language | English |
|---|---|
| Pages (from-to) | 200-207 |
| Number of pages | 8 |
| Journal | Journal of Molecular Catalysis A: Chemical |
| Volume | 256 |
| Issue number | 1-2 |
| DOIs | |
| Publication status | Published - Aug 18 2006 |
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Keywords
- Dehydrogenation
- Kinetics of dehydrogenation
- Oligomers
- Pincer Ir complexes
- Polyolefins
ASJC Scopus subject areas
- Catalysis
- Process Chemistry and Technology
- Materials Science (miscellaneous)
Cite this
Catalytic post-modification of alkene polymers. Chemistry and kinetics of dehydrogenation of alkene polymers and oligomers with pincer Ir complexes. / Ray, Amlan; Kissin, Yury V.; Zhu, Keming; Goldman, Alan S; Cherian, Anna E.; Coates, Geoffrey W.
In: Journal of Molecular Catalysis A: Chemical, Vol. 256, No. 1-2, 18.08.2006, p. 200-207.Research output: Contribution to journal › Article
}
TY - JOUR
T1 - Catalytic post-modification of alkene polymers. Chemistry and kinetics of dehydrogenation of alkene polymers and oligomers with pincer Ir complexes
AU - Ray, Amlan
AU - Kissin, Yury V.
AU - Zhu, Keming
AU - Goldman, Alan S
AU - Cherian, Anna E.
AU - Coates, Geoffrey W.
PY - 2006/8/18
Y1 - 2006/8/18
N2 - The paper presents details of catalytic dehydrogenation reactions of two high molecular weight, highly branched hydrocarbons, a polymer of 1-hexene and an oligomer of 1-butene, and describes kinetic analysis of these reactions. The dehydrogenation reactions were catalyzed with two pincer Ir complexes, [4-methoxy-2,6-C6H3(CH2P-tert-Bu2)2]IrH2 and [4-methoxy-2,6-C6H2(CH2P-iso-Pr2)2]IrH2, and were carried out at 150 °C in p-xylene solutions with norbornene as a hydrogen acceptor. The structure of all dehydrogenation reaction products and the Ir species was determined by 1H and 31P NMR. Mechanistically, these reactions are similar to dehydrogenation reactions of low molecular weight alkanes. Kinetic analysis of the reactions yielded the values of effective rate constants for all major reaction steps in the catalytic cycle. The results show that catalytic dehydrogenation of branched polymers in the presence of an alkene hydrogen acceptor is feasible at increased temperatures and represents a viable route to post-synthetic modification of branched polyolefins.
AB - The paper presents details of catalytic dehydrogenation reactions of two high molecular weight, highly branched hydrocarbons, a polymer of 1-hexene and an oligomer of 1-butene, and describes kinetic analysis of these reactions. The dehydrogenation reactions were catalyzed with two pincer Ir complexes, [4-methoxy-2,6-C6H3(CH2P-tert-Bu2)2]IrH2 and [4-methoxy-2,6-C6H2(CH2P-iso-Pr2)2]IrH2, and were carried out at 150 °C in p-xylene solutions with norbornene as a hydrogen acceptor. The structure of all dehydrogenation reaction products and the Ir species was determined by 1H and 31P NMR. Mechanistically, these reactions are similar to dehydrogenation reactions of low molecular weight alkanes. Kinetic analysis of the reactions yielded the values of effective rate constants for all major reaction steps in the catalytic cycle. The results show that catalytic dehydrogenation of branched polymers in the presence of an alkene hydrogen acceptor is feasible at increased temperatures and represents a viable route to post-synthetic modification of branched polyolefins.
KW - Dehydrogenation
KW - Kinetics of dehydrogenation
KW - Oligomers
KW - Pincer Ir complexes
KW - Polyolefins
UR - http://www.scopus.com/inward/record.url?scp=33747376690&partnerID=8YFLogxK
UR - http://www.scopus.com/inward/citedby.url?scp=33747376690&partnerID=8YFLogxK
U2 - 10.1016/j.molcata.2006.04.017
DO - 10.1016/j.molcata.2006.04.017
M3 - Article
AN - SCOPUS:33747376690
VL - 256
SP - 200
EP - 207
JO - Journal of Molecular Catalysis A: Chemical
JF - Journal of Molecular Catalysis A: Chemical
SN - 1381-1169
IS - 1-2
ER -