In Situ High-Pressure 31P{1H} NMR Studies of the Hydroformylation of 1-Hexene by RhH(CO)(PPh3)3

Claudio Bianchini; Hon Man Lee; Andrea Meli; Francesco Vizza

In Situ High-Pressure ³¹P{¹H} NMR Studies of the Hydroformylation of 1-Hexene by RhH(CO)(PPh₃)₃

Claudio Bianchini, Hon Man Lee, Andrea Meli, Francesco Vizza

Department of Chemistry

Research output: Contribution to journal › Article › peer-review

70 Citations (Scopus)

Abstract

The hydroformylation of 1-hexene with syngas (40 bar of 1:1 CO/H₂) in the presence of the catalyst precursor RhH(CO)(PPh₃)₃ has been studied by high-pressure NMR spectroscopy in a 10 mm sapphire tube equipped with a Ti-alloy valve. Except for RhH(CO)₂(PPh₃)₂, no direct observation of labile intermediates involved in the catalytic cycle has been detected; however as many as four rhodium resting states have been seen, and some factors controlling their formation/interconversion/inhibition have been identified. The information gathered from this in situ investigation is particularly relevant to a better understanding of the inhibiting action of the CO pressure as well as the positive action of PPh₃ addition.

Original language	English
Pages (from-to)	849-852
Number of pages	4
Journal	Organometallics
Volume	19
Issue number	5
Publication status	Published - 2000 Mar 6

All Science Journal Classification (ASJC) codes

Physical and Theoretical Chemistry
Organic Chemistry
Inorganic Chemistry

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title = "In Situ High-Pressure 31P{1H} NMR Studies of the Hydroformylation of 1-Hexene by RhH(CO)(PPh3)3",

abstract = "The hydroformylation of 1-hexene with syngas (40 bar of 1:1 CO/H2) in the presence of the catalyst precursor RhH(CO)(PPh3)3 has been studied by high-pressure NMR spectroscopy in a 10 mm sapphire tube equipped with a Ti-alloy valve. Except for RhH(CO)2(PPh3)2, no direct observation of labile intermediates involved in the catalytic cycle has been detected; however as many as four rhodium resting states have been seen, and some factors controlling their formation/interconversion/inhibition have been identified. The information gathered from this in situ investigation is particularly relevant to a better understanding of the inhibiting action of the CO pressure as well as the positive action of PPh3 addition.",

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T1 - In Situ High-Pressure 31P{1H} NMR Studies of the Hydroformylation of 1-Hexene by RhH(CO)(PPh3)3

AU - Bianchini, Claudio

AU - Lee, Hon Man

AU - Meli, Andrea

AU - Vizza, Francesco

PY - 2000/3/6

Y1 - 2000/3/6

N2 - The hydroformylation of 1-hexene with syngas (40 bar of 1:1 CO/H2) in the presence of the catalyst precursor RhH(CO)(PPh3)3 has been studied by high-pressure NMR spectroscopy in a 10 mm sapphire tube equipped with a Ti-alloy valve. Except for RhH(CO)2(PPh3)2, no direct observation of labile intermediates involved in the catalytic cycle has been detected; however as many as four rhodium resting states have been seen, and some factors controlling their formation/interconversion/inhibition have been identified. The information gathered from this in situ investigation is particularly relevant to a better understanding of the inhibiting action of the CO pressure as well as the positive action of PPh3 addition.

AB - The hydroformylation of 1-hexene with syngas (40 bar of 1:1 CO/H2) in the presence of the catalyst precursor RhH(CO)(PPh3)3 has been studied by high-pressure NMR spectroscopy in a 10 mm sapphire tube equipped with a Ti-alloy valve. Except for RhH(CO)2(PPh3)2, no direct observation of labile intermediates involved in the catalytic cycle has been detected; however as many as four rhodium resting states have been seen, and some factors controlling their formation/interconversion/inhibition have been identified. The information gathered from this in situ investigation is particularly relevant to a better understanding of the inhibiting action of the CO pressure as well as the positive action of PPh3 addition.

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