Palladium-catalyzed nonalternating copolymerization of ethene and carbon monoxide

Scope and mechanism

Rong Luo, David K. Newsham, Ayusman Sen

Research output: Contribution to journalArticle

22 Citations (Scopus)

Abstract

A series of nonalternating ethene/carbon monoxide copolymers with very low carbon monoxide content were synthesized using a neutral palladium catalyst bearing a phosphine-sulfonate ligand. The ratio of the binding affinities of carbon monoxide and ethene to the palladium chelate complex (P SO3)-- PdCH2CH2C(O)CH 3 has been determined by NMR spectroscopy to be ∼50:1 at 25 °C. The migratory insertions of ethene and carbon monoxide into the palladium methyl complex (PSO3)-PdCH3(py) have also been examined by NMR spectroscopy, giving the following activation parameters: ΔG(25°C) = 21.7kcal mol-1 (ΔH = 17.7(1) kcal mol-1 and ΔS = -13.6(4) eu) for ethene insertion; ΔG (25°C) = 13.0 kcal mol-1(ΔH = 16.6(8) kcal mol-1 and ΔS = 20(434) eu) for carbon monoxide insertion. Our study suggests that the unusually small difference in ethene and carbon monoxide binding affinities plays an important role in determining the copolymer composition.

Original languageEnglish (US)
Pages (from-to)6994-7000
Number of pages7
JournalOrganometallics
Volume28
Issue number24
DOIs
StatePublished - Dec 28 2009

Fingerprint

Palladium
copolymerization
Carbon Monoxide
carbon monoxide
Copolymerization
palladium
insertion
phosphine
Nuclear magnetic resonance spectroscopy
affinity
copolymers
Bearings (structural)
Copolymers
nuclear magnetic resonance
sulfonates
chelates
phosphines
spectroscopy
ethylene
Chemical activation

All Science Journal Classification (ASJC) codes

  • Organic Chemistry
  • Physical and Theoretical Chemistry
  • Inorganic Chemistry

Cite this

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title = "Palladium-catalyzed nonalternating copolymerization of ethene and carbon monoxide: Scope and mechanism",
abstract = "A series of nonalternating ethene/carbon monoxide copolymers with very low carbon monoxide content were synthesized using a neutral palladium catalyst bearing a phosphine-sulfonate ligand. The ratio of the binding affinities of carbon monoxide and ethene to the palladium chelate complex (P ∩SO3)-- PdCH2CH2C(O)CH 3 has been determined by NMR spectroscopy to be ∼50:1 at 25 °C. The migratory insertions of ethene and carbon monoxide into the palladium methyl complex (P∩SO3)-PdCH3(py) have also been examined by NMR spectroscopy, giving the following activation parameters: ΔG‡(25°C) = 21.7kcal mol-1 (ΔH‡ = 17.7(1) kcal mol-1 and ΔS ‡ = -13.6(4) eu) for ethene insertion; ΔG ‡(25°C) = 13.0 kcal mol-1(ΔH ‡ = 16.6(8) kcal mol-1 and ΔS ‡ = 20(434) eu) for carbon monoxide insertion. Our study suggests that the unusually small difference in ethene and carbon monoxide binding affinities plays an important role in determining the copolymer composition.",
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Palladium-catalyzed nonalternating copolymerization of ethene and carbon monoxide : Scope and mechanism. / Luo, Rong; Newsham, David K.; Sen, Ayusman.

In: Organometallics, Vol. 28, No. 24, 28.12.2009, p. 6994-7000.

Research output: Contribution to journalArticle

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