High-Pressure Infrared Studies of Rhodium Complexes Containing Thiolate Bridge Ligands under Hydroformylation Conditions
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- 作者：Montserrat Dié ; guez ; Carmen Claver ; Anna M. Masdeu-Bultó ; Aurora Ruiz ; Piet W. N. M. van Leeuwen ; and Gerard C. Schoemaker
- 刊名：Organometallics
- 出版年：1999
- 出版时间：May 24, 1999
- 年：1999
- 卷：18
- 期：11
- 页码：2107 - 2115
- 全文大小：238K
- 年卷期：v.18,no.11(May 24, 1999)
- ISSN：1520-6041
文摘
In situ high-pressure IR spectroscopy studies of the rhodium catalyst systems [Rh2{
ntities/mgr.gif">-S(CH2)3N(Me2)}2(COD)2]/PR3 (R = Ph, OPh), [Rh2{ntities/mgr.gif">-S(CH2)2S}(COD)2]/PPh3, [Rh2{ntities/mgr.gif">-S(CH2)4S}(COD)2]2/PPh3, [Rh2{ntities/mgr.gif">-XANTOSS}(COD)2]2/PPh3, and [Rh(acac)(CO)2]/PR3 (R = Ph, OPh)revealed the presence of mononuclear rhodium hydride species under hydroformylationconditions (80 ntities/deg.gif">C, 5-30 bar). The activities and selectivities, obtained during the hydroformylation of 1-hexene using these systems as catalyst precursors, can be fully accountedfor by the mononuclear species observed. Deuterioformylation experiments using dinuclear[Rh2{ntities/mgr.gif">-S(CH2)3N(Me2)}2(COD)2]/PR3 systems lent no support to a dinuclear mechanism.
ntities/mgr.gif">-S(CH2)3N(Me2)}2(COD)2]/PR3 (R = Ph, OPh), [Rh2{ntities/mgr.gif">-S(CH2)2S}(COD)2]/PPh3, [Rh2{ntities/mgr.gif">-S(CH2)4S}(COD)2]2/PPh3, [Rh2{ntities/mgr.gif">-XANTOSS}(COD)2]2/PPh3, and [Rh(acac)(CO)2]/PR3 (R = Ph, OPh)revealed the presence of mononuclear rhodium hydride species under hydroformylationconditions (80 ntities/deg.gif">C, 5-30 bar). The activities and selectivities, obtained during the hydroformylation of 1-hexene using these systems as catalyst precursors, can be fully accountedfor by the mononuclear species observed. Deuterioformylation experiments using dinuclear[Rh2{ntities/mgr.gif">-S(CH2)3N(Me2)}2(COD)2]/PR3 systems lent no support to a dinuclear mechanism.