Abstract
A series of oligomeric methylsiloxane compounds functionalized with pyridyl groups was synthesized and used as ligands in the aerobic Pd(OAc) 2-catalyzed oxidation of benzyl alcohol to benzaldehyde at 353 K. The effect of tethering two pyridine ligands at the terminal positions of linear siloxanes of varying length was systematically investigated, as was the effect of the attachment point of the pyridine ring (meta or para). It was found that meta-substituted pyridylsiloxanes were generally more effective in protecting the catalyst against Pd agglomeration. For this purpose, the optimal meta-pyridylsiloxane ligands had 4-6 silicon atoms or 10 silicon atoms for para-pyridylsiloxane ligands. The metal-ligand binding properties were used to interpret the catalytic behavior, and the ability of the catalyst stability correlated with ability of the bis-pyridyl ligand to form a mononuclear cyclic complex with Pd.
| Original language | English |
|---|---|
| Pages (from-to) | 297-304 |
| Number of pages | 8 |
| Journal | Applied Catalysis A: General |
| Volume | 391 |
| Issue number | 1-2 |
| DOIs | |
| Publication status | Published - Jan 4 2011 |
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Keywords
- Ligand tethering
- Partial oxidation
- Pd(II) catalysis
- Pyridylsiloxane
ASJC Scopus subject areas
- Catalysis
- Process Chemistry and Technology
Cite this
Bis(pyridyl)siloxane-Pd(II) complex catalyzed oxidation of alcohol to aldehyde : Effect of ligand tethering on catalytic activity and deactivation behavior. / Missaghi, Michael N.; Galloway, John M.; Kung, Harold H.
In: Applied Catalysis A: General, Vol. 391, No. 1-2, 04.01.2011, p. 297-304.Research output: Contribution to journal › Article
}
TY - JOUR
T1 - Bis(pyridyl)siloxane-Pd(II) complex catalyzed oxidation of alcohol to aldehyde
T2 - Effect of ligand tethering on catalytic activity and deactivation behavior
AU - Missaghi, Michael N.
AU - Galloway, John M.
AU - Kung, Harold H
PY - 2011/1/4
Y1 - 2011/1/4
N2 - A series of oligomeric methylsiloxane compounds functionalized with pyridyl groups was synthesized and used as ligands in the aerobic Pd(OAc) 2-catalyzed oxidation of benzyl alcohol to benzaldehyde at 353 K. The effect of tethering two pyridine ligands at the terminal positions of linear siloxanes of varying length was systematically investigated, as was the effect of the attachment point of the pyridine ring (meta or para). It was found that meta-substituted pyridylsiloxanes were generally more effective in protecting the catalyst against Pd agglomeration. For this purpose, the optimal meta-pyridylsiloxane ligands had 4-6 silicon atoms or 10 silicon atoms for para-pyridylsiloxane ligands. The metal-ligand binding properties were used to interpret the catalytic behavior, and the ability of the catalyst stability correlated with ability of the bis-pyridyl ligand to form a mononuclear cyclic complex with Pd.
AB - A series of oligomeric methylsiloxane compounds functionalized with pyridyl groups was synthesized and used as ligands in the aerobic Pd(OAc) 2-catalyzed oxidation of benzyl alcohol to benzaldehyde at 353 K. The effect of tethering two pyridine ligands at the terminal positions of linear siloxanes of varying length was systematically investigated, as was the effect of the attachment point of the pyridine ring (meta or para). It was found that meta-substituted pyridylsiloxanes were generally more effective in protecting the catalyst against Pd agglomeration. For this purpose, the optimal meta-pyridylsiloxane ligands had 4-6 silicon atoms or 10 silicon atoms for para-pyridylsiloxane ligands. The metal-ligand binding properties were used to interpret the catalytic behavior, and the ability of the catalyst stability correlated with ability of the bis-pyridyl ligand to form a mononuclear cyclic complex with Pd.
KW - Ligand tethering
KW - Partial oxidation
KW - Pd(II) catalysis
KW - Pyridylsiloxane
UR - http://www.scopus.com/inward/record.url?scp=78650857647&partnerID=8YFLogxK
UR - http://www.scopus.com/inward/citedby.url?scp=78650857647&partnerID=8YFLogxK
U2 - 10.1016/j.apcata.2010.09.008
DO - 10.1016/j.apcata.2010.09.008
M3 - Article
AN - SCOPUS:78650857647
VL - 391
SP - 297
EP - 304
JO - Applied Catalysis A: General
JF - Applied Catalysis A: General
SN - 0926-860X
IS - 1-2
ER -