Styrene Production from Benzene and Ethylene Catalyzed by Palladium(II): Enhancement of Selectivity toward Styrene via Temperature-dependent Vinyl Ester Consumption

Xiaofan Jia; Aisling M. Foley; Chang Liu; Benjamin A. Vaughan; Bradley A. McKeown; Sen Zhang; T. Brent Gunnoe

doi:10.1021/acs.organomet.9b00349

Styrene Production from Benzene and Ethylene Catalyzed by Palladium(II): Enhancement of Selectivity toward Styrene via Temperature-dependent Vinyl Ester Consumption

Xiaofan Jia
, Aisling M. Foley
, Chang Liu
, Benjamin A. Vaughan
, Bradley A. McKeown
, Sen Zhang
, T. Brent Gunnoe

Surface Chemistry & Catalysis Group

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

20 Scopus citations

Abstract

Oxidative ethylene hydrophenylation catalyzed by palladium(II) acetate with Cu(II) oxidants to produce styrene generally suffers from low selectivity and/or low yield. Commonly observed side products include vinyl carboxylates and stilbene. In this Article, the selectivity for styrene formation by Pd(OAc)₂ is studied as a function of reaction temperature, ethylene pressure, Brønsted acid additive, Cu(II) oxidant amount, and oxygen pressure. Under optimized conditions, at high temperatures (180 °C) and low olefin pressure (20 psig), nearly quantitative yield (>95%) of styrene is produced based on the limiting reagent copper(II) pivalate. We propose the selectivity for styrene versus vinyl pivalate at 180 °C is due to a palladium-catalyzed conversion of benzene and in situ formed vinyl pivalate to styrene.

Original language	English
Pages (from-to)	3532-3541
Number of pages	10
Journal	Organometallics
Volume	38
Issue number	19
DOIs	https://doi.org/10.1021/acs.organomet.9b00349
State	Published - Oct 14 2019

Funding

This work was supported by the U.S. Department of Energy, Office of Basic Energy Sciences, Chemical Sciences, Geosciences, and Biosciences Division (DE-SC0000776).

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10.1021/acs.organomet.9b00349

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title = "Styrene Production from Benzene and Ethylene Catalyzed by Palladium(II): Enhancement of Selectivity toward Styrene via Temperature-dependent Vinyl Ester Consumption",

abstract = "Oxidative ethylene hydrophenylation catalyzed by palladium(II) acetate with Cu(II) oxidants to produce styrene generally suffers from low selectivity and/or low yield. Commonly observed side products include vinyl carboxylates and stilbene. In this Article, the selectivity for styrene formation by Pd(OAc)2 is studied as a function of reaction temperature, ethylene pressure, Br{\o}nsted acid additive, Cu(II) oxidant amount, and oxygen pressure. Under optimized conditions, at high temperatures (180 °C) and low olefin pressure (20 psig), nearly quantitative yield (>95\%) of styrene is produced based on the limiting reagent copper(II) pivalate. We propose the selectivity for styrene versus vinyl pivalate at 180 °C is due to a palladium-catalyzed conversion of benzene and in situ formed vinyl pivalate to styrene.",

author = "Xiaofan Jia and Foley, \{Aisling M.\} and Chang Liu and Vaughan, \{Benjamin A.\} and McKeown, \{Bradley A.\} and Sen Zhang and Gunnoe, \{T. Brent\}",

note = "Publisher Copyright: Copyright {\textcopyright} 2019 American Chemical Society.",

year = "2019",

month = oct,

day = "14",

doi = "10.1021/acs.organomet.9b00349",

language = "English",

volume = "38",

pages = "3532--3541",

journal = "Organometallics",

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TY - JOUR

T1 - Styrene Production from Benzene and Ethylene Catalyzed by Palladium(II)

T2 - Enhancement of Selectivity toward Styrene via Temperature-dependent Vinyl Ester Consumption

AU - Jia, Xiaofan

AU - Foley, Aisling M.

AU - Liu, Chang

AU - Vaughan, Benjamin A.

AU - McKeown, Bradley A.

AU - Zhang, Sen

AU - Gunnoe, T. Brent

PY - 2019/10/14

Y1 - 2019/10/14

N2 - Oxidative ethylene hydrophenylation catalyzed by palladium(II) acetate with Cu(II) oxidants to produce styrene generally suffers from low selectivity and/or low yield. Commonly observed side products include vinyl carboxylates and stilbene. In this Article, the selectivity for styrene formation by Pd(OAc)2 is studied as a function of reaction temperature, ethylene pressure, Brønsted acid additive, Cu(II) oxidant amount, and oxygen pressure. Under optimized conditions, at high temperatures (180 °C) and low olefin pressure (20 psig), nearly quantitative yield (>95%) of styrene is produced based on the limiting reagent copper(II) pivalate. We propose the selectivity for styrene versus vinyl pivalate at 180 °C is due to a palladium-catalyzed conversion of benzene and in situ formed vinyl pivalate to styrene.

AB - Oxidative ethylene hydrophenylation catalyzed by palladium(II) acetate with Cu(II) oxidants to produce styrene generally suffers from low selectivity and/or low yield. Commonly observed side products include vinyl carboxylates and stilbene. In this Article, the selectivity for styrene formation by Pd(OAc)2 is studied as a function of reaction temperature, ethylene pressure, Brønsted acid additive, Cu(II) oxidant amount, and oxygen pressure. Under optimized conditions, at high temperatures (180 °C) and low olefin pressure (20 psig), nearly quantitative yield (>95%) of styrene is produced based on the limiting reagent copper(II) pivalate. We propose the selectivity for styrene versus vinyl pivalate at 180 °C is due to a palladium-catalyzed conversion of benzene and in situ formed vinyl pivalate to styrene.

UR - https://www.scopus.com/pages/publications/85071906899

U2 - 10.1021/acs.organomet.9b00349

DO - 10.1021/acs.organomet.9b00349

M3 - Article

AN - SCOPUS:85071906899

SN - 0276-7333

VL - 38

SP - 3532

EP - 3541

JO - Organometallics

JF - Organometallics

IS - 19

ER -

Styrene Production from Benzene and Ethylene Catalyzed by Palladium(II): Enhancement of Selectivity toward Styrene via Temperature-dependent Vinyl Ester Consumption

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