Electrophilic RhI catalysts for arene H/D exchange in acidic media: Evidence for an electrophilic aromatic substitution mechanism

Michael S. Webster-Gardiner; Paige E. Piszel; Ross Fu; Bradley A. McKeown; Robert J. Nielsen; William A. Goddard; T. Brent Gunnoe

doi:10.1016/j.molcata.2016.07.045

Electrophilic Rh^I catalysts for arene H/D exchange in acidic media: Evidence for an electrophilic aromatic substitution mechanism

Michael S. Webster-Gardiner
, Paige E. Piszel
, Ross Fu
, Bradley A. McKeown
, Robert J. Nielsen
, William A. Goddard
, T. Brent Gunnoe

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

Abstract

A series of new rhodium (I) complexes supported by bidentate nitrogen-donor ligands with varying electronic and steric properties were synthesized in situ and evaluated for catalytic arene C–H/D activation. In trifluoroacetic acid (HTFA), these complexes are proposed to mediate H/D exchange of arene C–H/D bonds by an electrophilic aromatic substitution mechanism that involves Rh-mediated activation of HTFA (or DTFA). DFT calculations support the proposed pathway for the H/D exchange reactions.

Original language	English
Pages (from-to)	381-388
Number of pages	8
Journal	Journal of Molecular Catalysis A: Chemical
Volume	426
DOIs	https://doi.org/10.1016/j.molcata.2016.07.045
Publication status	Published - 1 Jan 2017
Externally published	Yes

Keywords

Acid
Arene
C–H activation
Electrophilic
Rhodium

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10.1016/j.molcata.2016.07.045

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title = "Electrophilic RhI catalysts for arene H/D exchange in acidic media: Evidence for an electrophilic aromatic substitution mechanism",

abstract = "A series of new rhodium (I) complexes supported by bidentate nitrogen-donor ligands with varying electronic and steric properties were synthesized in situ and evaluated for catalytic arene C–H/D activation. In trifluoroacetic acid (HTFA), these complexes are proposed to mediate H/D exchange of arene C–H/D bonds by an electrophilic aromatic substitution mechanism that involves Rh-mediated activation of HTFA (or DTFA). DFT calculations support the proposed pathway for the H/D exchange reactions.",

keywords = "Acid, Arene, C–H activation, Electrophilic, Rhodium",

author = "Webster-Gardiner, \{Michael S.\} and Piszel, \{Paige E.\} and Ross Fu and McKeown, \{Bradley A.\} and Nielsen, \{Robert J.\} and Goddard, \{William A.\} and Gunnoe, \{T. Brent\}",

note = "Publisher Copyright: {\textcopyright} 2016 Elsevier B.V.",

year = "2017",

month = jan,

day = "1",

doi = "10.1016/j.molcata.2016.07.045",

language = "English",

volume = "426",

pages = "381--388",

journal = "Journal of Molecular Catalysis A: Chemical",

issn = "1381-1169",

}

TY - JOUR

T1 - Electrophilic RhI catalysts for arene H/D exchange in acidic media

T2 - Evidence for an electrophilic aromatic substitution mechanism

AU - Webster-Gardiner, Michael S.

AU - Piszel, Paige E.

AU - Fu, Ross

AU - McKeown, Bradley A.

AU - Nielsen, Robert J.

AU - Goddard, William A.

AU - Gunnoe, T. Brent

PY - 2017/1/1

Y1 - 2017/1/1

N2 - A series of new rhodium (I) complexes supported by bidentate nitrogen-donor ligands with varying electronic and steric properties were synthesized in situ and evaluated for catalytic arene C–H/D activation. In trifluoroacetic acid (HTFA), these complexes are proposed to mediate H/D exchange of arene C–H/D bonds by an electrophilic aromatic substitution mechanism that involves Rh-mediated activation of HTFA (or DTFA). DFT calculations support the proposed pathway for the H/D exchange reactions.

AB - A series of new rhodium (I) complexes supported by bidentate nitrogen-donor ligands with varying electronic and steric properties were synthesized in situ and evaluated for catalytic arene C–H/D activation. In trifluoroacetic acid (HTFA), these complexes are proposed to mediate H/D exchange of arene C–H/D bonds by an electrophilic aromatic substitution mechanism that involves Rh-mediated activation of HTFA (or DTFA). DFT calculations support the proposed pathway for the H/D exchange reactions.

KW - Acid

KW - Arene

KW - C–H activation

KW - Electrophilic

KW - Rhodium

UR - https://www.scopus.com/pages/publications/84981742766

U2 - 10.1016/j.molcata.2016.07.045

DO - 10.1016/j.molcata.2016.07.045

M3 - Article

AN - SCOPUS:84981742766

SN - 1381-1169

VL - 426

SP - 381

EP - 388

JO - Journal of Molecular Catalysis A: Chemical

JF - Journal of Molecular Catalysis A: Chemical

ER -

Electrophilic Rh^I catalysts for arene H/D exchange in acidic media: Evidence for an electrophilic aromatic substitution mechanism

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Keywords

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