High-pressure NMR studies on the alternating copolymerization of propene with carbon monoxide catalyzed by a palladium(II) complex of an unsymmetrical phosphine-phosphite ligand

Kyoko Nozaki, Tamejiro Hiyama, Smita Kacker, I. Horváth

Research output: Contribution to journalArticle

29 Citations (Scopus)

Abstract

When high-pressure NMR techniques are employed, the following two facts are revealed. (1) The cis/trans isomerization from (SP-4-4)-[Pt(CH3)(CO)(L1)][BAr4] (8a; L1 = (R,S)-BINAPHOS; Ar = 3,5-(CF3)2C6H3) to the more stable SP-4-3 isomer (8b) is faster than CO insertion into either 8a or 8b, the CO insertion being reversible. (2) For the Pd11-L1-catalyzed copolymerization of propene and CO, there exist at least two major resting states, most probably acylpalladium, (SP-4-3)-[Pd(COR)(L2)(L1)][BAr4] (3; L2 = CH3CN, CO), and alkyl-palladium, [Pd{CH2CH(CH3)C(=O)R}(L1)][BAr4] (5a).

Original languageEnglish
Pages (from-to)2031-2035
Number of pages5
JournalOrganometallics
Volume19
Issue number10
Publication statusPublished - May 15 2000

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phosphine
Phosphites
Palladium
copolymerization
Carbon Monoxide
phosphines
carbon monoxide
Copolymerization
palladium
insertion
Nuclear magnetic resonance
Ligands
nuclear magnetic resonance
ligands
isomerization
isomers
Isomerization
Isomers
propylene

ASJC Scopus subject areas

  • Inorganic Chemistry
  • Organic Chemistry

Cite this

High-pressure NMR studies on the alternating copolymerization of propene with carbon monoxide catalyzed by a palladium(II) complex of an unsymmetrical phosphine-phosphite ligand. / Nozaki, Kyoko; Hiyama, Tamejiro; Kacker, Smita; Horváth, I.

In: Organometallics, Vol. 19, No. 10, 15.05.2000, p. 2031-2035.

Research output: Contribution to journalArticle

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abstract = "When high-pressure NMR techniques are employed, the following two facts are revealed. (1) The cis/trans isomerization from (SP-4-4)-[Pt(CH3)(CO)(L1)][BAr4] (8a; L1 = (R,S)-BINAPHOS; Ar = 3,5-(CF3)2C6H3) to the more stable SP-4-3 isomer (8b) is faster than CO insertion into either 8a or 8b, the CO insertion being reversible. (2) For the Pd11-L1-catalyzed copolymerization of propene and CO, there exist at least two major resting states, most probably acylpalladium, (SP-4-3)-[Pd(COR)(L2)(L1)][BAr4] (3; L2 = CH3CN, CO), and alkyl-palladium, [Pd{CH2CH(CH3)C(=O)R}(L1)][BAr4] (5a).",
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AU - Nozaki, Kyoko

AU - Hiyama, Tamejiro

AU - Kacker, Smita

AU - Horváth, I.

PY - 2000/5/15

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N2 - When high-pressure NMR techniques are employed, the following two facts are revealed. (1) The cis/trans isomerization from (SP-4-4)-[Pt(CH3)(CO)(L1)][BAr4] (8a; L1 = (R,S)-BINAPHOS; Ar = 3,5-(CF3)2C6H3) to the more stable SP-4-3 isomer (8b) is faster than CO insertion into either 8a or 8b, the CO insertion being reversible. (2) For the Pd11-L1-catalyzed copolymerization of propene and CO, there exist at least two major resting states, most probably acylpalladium, (SP-4-3)-[Pd(COR)(L2)(L1)][BAr4] (3; L2 = CH3CN, CO), and alkyl-palladium, [Pd{CH2CH(CH3)C(=O)R}(L1)][BAr4] (5a).

AB - When high-pressure NMR techniques are employed, the following two facts are revealed. (1) The cis/trans isomerization from (SP-4-4)-[Pt(CH3)(CO)(L1)][BAr4] (8a; L1 = (R,S)-BINAPHOS; Ar = 3,5-(CF3)2C6H3) to the more stable SP-4-3 isomer (8b) is faster than CO insertion into either 8a or 8b, the CO insertion being reversible. (2) For the Pd11-L1-catalyzed copolymerization of propene and CO, there exist at least two major resting states, most probably acylpalladium, (SP-4-3)-[Pd(COR)(L2)(L1)][BAr4] (3; L2 = CH3CN, CO), and alkyl-palladium, [Pd{CH2CH(CH3)C(=O)R}(L1)][BAr4] (5a).

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