Abstract
A series of new ( t Bu2PSCOPR2)IrHCl iridium complexes with 'hybrid' phosphinothious-phosphinite PSCOP ligands ([ t Bu2PSCOPR2 =1-(SPtBu2)-3-(OPR2)-C6H4], R= tBu, 4a, R=Cy, 4b, R= iPr, 4c, and R=Et, 4d) have been synthesized and characterized. Treatment of complexes 4a-d with sodium tert-butoxide generates the active species for catalytic transfer-dehydrogenation of cyclooctane (COA) or n-octane using tert-butylethylene (TBE) as hydrogen acceptor to form cyclooctene (COE) or octenes, respectively. The catalytic activity of these complexes and the product selectivity in alkane dehydrogenation is greatly influenced by the steric properties of the pincer ligand. In general, the less sterically bulky complex exhibits higher catalytic activity than the more hindered complex. Among the new (PSCOP)Ir-type complexes, the least crowded complex ( t Bu2PSCOPEt2)IrHCl 4d is most active for n-octane/TBE transfer-dehydrogenation. The relatively crowded, less active, complexes ( t Bu2PSCOP t Bu2)IrHCl (4a) and ( t Bu2PSCOPCy2)IrHCl (4b) exhibit high regioselectivity for α-olefin formation at the early stages of the reaction.
| Original language | English |
|---|---|
| Journal | Polyhedron |
| DOIs | |
| Publication status | Accepted/In press - Jan 19 2016 |
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Keywords
- Alkane
- Alkene
- Dehydrogenation
- Homogeneous catalysis
- Iridium
ASJC Scopus subject areas
- Inorganic Chemistry
- Materials Chemistry
- Physical and Theoretical Chemistry
Cite this
Catalytic alkane transfer-dehydrogenation by PSCOP iridium pincer complexes. / Yao, Wubing; Jia, Xiangqing; Leng, Xuebing; Goldman, Alan S; Brookhart, Maurice; Huang, Zheng.
In: Polyhedron, 19.01.2016.Research output: Contribution to journal › Article
}
TY - JOUR
T1 - Catalytic alkane transfer-dehydrogenation by PSCOP iridium pincer complexes
AU - Yao, Wubing
AU - Jia, Xiangqing
AU - Leng, Xuebing
AU - Goldman, Alan S
AU - Brookhart, Maurice
AU - Huang, Zheng
PY - 2016/1/19
Y1 - 2016/1/19
N2 - A series of new ( t Bu2PSCOPR2)IrHCl iridium complexes with 'hybrid' phosphinothious-phosphinite PSCOP ligands ([ t Bu2PSCOPR2 =1-(SPtBu2)-3-(OPR2)-C6H4], R= tBu, 4a, R=Cy, 4b, R= iPr, 4c, and R=Et, 4d) have been synthesized and characterized. Treatment of complexes 4a-d with sodium tert-butoxide generates the active species for catalytic transfer-dehydrogenation of cyclooctane (COA) or n-octane using tert-butylethylene (TBE) as hydrogen acceptor to form cyclooctene (COE) or octenes, respectively. The catalytic activity of these complexes and the product selectivity in alkane dehydrogenation is greatly influenced by the steric properties of the pincer ligand. In general, the less sterically bulky complex exhibits higher catalytic activity than the more hindered complex. Among the new (PSCOP)Ir-type complexes, the least crowded complex ( t Bu2PSCOPEt2)IrHCl 4d is most active for n-octane/TBE transfer-dehydrogenation. The relatively crowded, less active, complexes ( t Bu2PSCOP t Bu2)IrHCl (4a) and ( t Bu2PSCOPCy2)IrHCl (4b) exhibit high regioselectivity for α-olefin formation at the early stages of the reaction.
AB - A series of new ( t Bu2PSCOPR2)IrHCl iridium complexes with 'hybrid' phosphinothious-phosphinite PSCOP ligands ([ t Bu2PSCOPR2 =1-(SPtBu2)-3-(OPR2)-C6H4], R= tBu, 4a, R=Cy, 4b, R= iPr, 4c, and R=Et, 4d) have been synthesized and characterized. Treatment of complexes 4a-d with sodium tert-butoxide generates the active species for catalytic transfer-dehydrogenation of cyclooctane (COA) or n-octane using tert-butylethylene (TBE) as hydrogen acceptor to form cyclooctene (COE) or octenes, respectively. The catalytic activity of these complexes and the product selectivity in alkane dehydrogenation is greatly influenced by the steric properties of the pincer ligand. In general, the less sterically bulky complex exhibits higher catalytic activity than the more hindered complex. Among the new (PSCOP)Ir-type complexes, the least crowded complex ( t Bu2PSCOPEt2)IrHCl 4d is most active for n-octane/TBE transfer-dehydrogenation. The relatively crowded, less active, complexes ( t Bu2PSCOP t Bu2)IrHCl (4a) and ( t Bu2PSCOPCy2)IrHCl (4b) exhibit high regioselectivity for α-olefin formation at the early stages of the reaction.
KW - Alkane
KW - Alkene
KW - Dehydrogenation
KW - Homogeneous catalysis
KW - Iridium
UR - http://www.scopus.com/inward/record.url?scp=84975528004&partnerID=8YFLogxK
UR - http://www.scopus.com/inward/citedby.url?scp=84975528004&partnerID=8YFLogxK
U2 - 10.1016/j.poly.2016.02.044
DO - 10.1016/j.poly.2016.02.044
M3 - Article
JO - Polyhedron
JF - Polyhedron
SN - 0277-5387
ER -