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; István T. Horváth

doi:10.1021/om990985x

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
, István T. Horváth

Research output: Journal Publications and Reviews › RGC 21 - Publication in refereed journal › peer-review

33 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).

© 2000 American Chemical Society

Original language	English
Pages (from-to)	2031-2035
Journal	Organometallics
Volume	19
Issue number	10
DOIs	https://doi.org/10.1021/om990985x
Publication status	Published - 15 May 2000
Externally published	Yes

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title = "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",

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). {\textcopyright} 2000 American Chemical Society",

author = "Kyoko Nozaki and Tamejiro Hiyama and Smita Kacker and Horv{\'a}th, \{Istv{\'a}n T.\}",

year = "2000",

month = may,

day = "15",

doi = "10.1021/om990985x",

language = "English",

volume = "19",

pages = "2031--2035",

journal = "Organometallics",

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

Research output: Journal Publications and Reviews › RGC 21 - Publication in refereed journal › peer-review

TY - JOUR

T1 - 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

AU - Nozaki, Kyoko

AU - Hiyama, Tamejiro

AU - Kacker, Smita

AU - Horváth, István T.

PY - 2000/5/15

Y1 - 2000/5/15

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). © 2000 American Chemical Society

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). © 2000 American Chemical Society

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U2 - 10.1021/om990985x

DO - 10.1021/om990985x

M3 - RGC 21 - Publication in refereed journal

SN - 0276-7333

VL - 19

SP - 2031

EP - 2035

JO - Organometallics

JF - Organometallics

IS - 10

ER -

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

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