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Title: Synthesis and Reactivity of Palladium(II) Alkyl Complexes that Contain Phosphine-cyclopentanesulfonate Ligands

Journal Article · · Organometallics
 [1]; ORCiD logo [1]
  1. Univ. of Chicago, IL (United States)
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The synthesis of the phosphine-cyclopentanesulfonate pro-ligands Li/K[2-PPh2-cyclopentanesulfonate] (Li/K[2a]), Li/K[2-P(2-OMe-Ph)2-cyclopentanesulfonate] (Li/K[2b]), and H[2b], and the corresponding Pd(II) alkyl complexes (κ2-P,O-2a)PdMe(pyridine) (3a) and (κ2-P,O-2b)PdMe(pyridine) (3b) is described herein. The sulfonate-bridged base-free dimer {(2b)PdMe}2 (4b) was synthesized by abstraction of pyridine from 3b using B(C6F5)3. The borane-coordinated base-free dimer [{2b·B(C6F5)3}PdMe]2 (5b), in which B(C6F5)3 binds to a sulfonate oxygen, was prepared by addition of 1 equiv of B(C6F5)3 per Pd to 4b or addition of 2 equiv of B(C6F5)3 to 3b. Compounds 3b, 4b, and 5b polymerize ethylene with low activity (up to 210 kg mol–1 h–1 at 250 psi and 80 °C) to linear polyethylene (Mn = 1950–5250 Da) with predominantly internal olefin placements. 3b and 4b copolymerize ethylene with methyl acrylate to linear copolymers that contain up to 11.7 mol % methyl acrylate, which is incorporated as –CH2CH(CO2Me)CH2– (80%) in-chain units and –CH2CH(CO2Me)Me (8%) and –CH2CH=CH(CO2Me) (12%) chain-end units. 3b and 4b also copolymerize ethylene with vinyl fluoride to linear copolymers that contain up to 0.41 mol % vinyl fluoride, which is incorporated as –CH2CHFCH2– (~80%) in-chain units and –CH2CF2H (7%), –CH2CHFCH3 (5%), and –CH2CH2F (8%) chain-end units. Complexes 3b and 4b are more stable and active in ethylene polymerization than analogous (PAr2-CH2CH2SO3)PdR catalysts, but are less active than analogous (PAr2-arenesulfonate)PdR catalysts. Low-temperature NMR studies show that 4b reacts with ethylene below -10 °C to form the ethylene adduct cis-P,R-(2b)PdMe(ethylene) (7b), which undergoes ethylene insertion at 5 °C. DFT calculations for a model (PMe2-cyclopentanesulfonate)Pd(Pr)(ethylene) species show that ethylene insertion proceeds by cis-P,R/trans-P,R isomerization followed by migratory insertion, and that the lower activity of 3b and 4b vis-à-vis analogous (PAr2-arenesulfonate)PdR catalysts results from a higher barrier for migratory insertion of the trans-P,R isomer.

Research Organization:
Argonne National Laboratory (ANL), Argonne, IL (United States). Advanced Photon Source (APS)
Sponsoring Organization:
National Science Foundation (NSF); US Department of Education; USDOE Office of Science (SC)
Grant/Contract Number:
CHE-0911180; CHE-1709159; CHE-1048528; P200A120093; ACI-1548562; AC02-06CH11357; NSF/CHE-1346572
OSTI ID:
1399121
Journal Information:
Organometallics, Vol. 36, Issue 17; ISSN 0276-7333
Publisher:
American Chemical SocietyCopyright Statement
Country of Publication:
United States
Language:
ENGLISH
Citation Metrics:
Cited by: 23 works
Citation information provided by
Web of Science

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Cited By (3)

Pd‐Iminocarboxylate Complexes and Their Behavior in Ethylene Polymerization journal December 2019
Indole-bridged bisphosphine-monoxide palladium catalysts for ethylene polymerization and copolymerization with polar monomers journal January 2020
Camphor-based phosphine-carbonyl ligands for Ni catalyzed ethylene oligomerization journal January 2020

Linked Research (8)

Figures / Tables (25)

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Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
Palladium
Hydrocarbons
Copolymerization
Catalysts
Molecular structure