Establishing the Role of Triflate Anions in H2 Activation by a Cationic Triorganotin(IV) Lewis Acid

Joshua Sapsford; Dániel Csókás; Daniel Scott; Roland Turnell-Ritson; Adam Piascik; Imre Pápai; Andrew Ashley

doi:10.1021/acscatal.0c02023

Establishing the Role of Triflate Anions in H₂ Activation by a Cationic Triorganotin(IV) Lewis Acid

Joshua Sapsford, Dániel Csókás, Daniel Scott, Roland Turnell-Ritson, Adam Piascik, Imre Pápai, Andrew Ashley

Department of Chemistry

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

4 Citations (SciVal)

Abstract

Cationic Lewis acids (LAs) are gaining interest as targets for frustrated Lewis pair (FLP)-mediated catalysis. Unlike neutral boranes, which are the most prevalent LAs for FLP hydrogenations, the Lewis acidity of cations can be tuned through modulation of the counteranion; however, detailed studies on such anion effects are currently lacking in the literature. Herein, we present experimental and computational studies which probe the mechanism of H₂ activation using iPr₃SnOTf (1-OTf) in conjunction with a coordinating (quinuclidine; qui) and noncoordinating (2,4,6-collidine; col) base and compare its reactivity with {iPr₃Sn·base}{Al[OC(CF₃)₃]₄} (base = qui/col) systems which lack a coordinating anion to investigate the active species responsible for H₂ activation and hence resolve any mechanistic roles for OTf^– in the iPr₃SnOTf-mediated pathway.

Original language	English
Pages (from-to)	7573–7583
Journal	ACS Catalysis
Volume	10
Issue number	14
Early online date	8 Jun 2020
DOIs	https://doi.org/10.1021/acscatal.0c02023
Publication status	Published - 17 Jul 2020

Access to Document

10.1021/acscatal.0c02023Licence: CC BY

Cite this

@article{c87d78460dcc44338c2d969fa95cc102,

title = "Establishing the Role of Triflate Anions in H2 Activation by a Cationic Triorganotin(IV) Lewis Acid",

abstract = "Cationic Lewis acids (LAs) are gaining interest as targets for frustrated Lewis pair (FLP)-mediated catalysis. Unlike neutral boranes, which are the most prevalent LAs for FLP hydrogenations, the Lewis acidity of cations can be tuned through modulation of the counteranion; however, detailed studies on such anion effects are currently lacking in the literature. Herein, we present experimental and computational studies which probe the mechanism of H2 activation using iPr3SnOTf (1-OTf) in conjunction with a coordinating (quinuclidine; qui) and noncoordinating (2,4,6-collidine; col) base and compare its reactivity with {iPr3Sn·base}{Al[OC(CF3)3]4} (base = qui/col) systems which lack a coordinating anion to investigate the active species responsible for H2 activation and hence resolve any mechanistic roles for OTf– in the iPr3SnOTf-mediated pathway.",

author = "Joshua Sapsford and D{\'a}niel Cs{\'o}k{\'a}s and Daniel Scott and Roland Turnell-Ritson and Adam Piascik and Imre P{\'a}pai and Andrew Ashley",

year = "2020",

month = jul,

day = "17",

doi = "10.1021/acscatal.0c02023",

language = "English",

volume = "10",

pages = "7573–7583",

journal = "ACS Catalysis",

issn = "2155-5435",

publisher = "American Chemical Society",

number = "14",

}

TY - JOUR

T1 - Establishing the Role of Triflate Anions in H2 Activation by a Cationic Triorganotin(IV) Lewis Acid

AU - Sapsford, Joshua

AU - Csókás, Dániel

AU - Scott, Daniel

AU - Turnell-Ritson, Roland

AU - Piascik, Adam

AU - Pápai, Imre

AU - Ashley, Andrew

PY - 2020/7/17

Y1 - 2020/7/17

N2 - Cationic Lewis acids (LAs) are gaining interest as targets for frustrated Lewis pair (FLP)-mediated catalysis. Unlike neutral boranes, which are the most prevalent LAs for FLP hydrogenations, the Lewis acidity of cations can be tuned through modulation of the counteranion; however, detailed studies on such anion effects are currently lacking in the literature. Herein, we present experimental and computational studies which probe the mechanism of H2 activation using iPr3SnOTf (1-OTf) in conjunction with a coordinating (quinuclidine; qui) and noncoordinating (2,4,6-collidine; col) base and compare its reactivity with {iPr3Sn·base}{Al[OC(CF3)3]4} (base = qui/col) systems which lack a coordinating anion to investigate the active species responsible for H2 activation and hence resolve any mechanistic roles for OTf– in the iPr3SnOTf-mediated pathway.

AB - Cationic Lewis acids (LAs) are gaining interest as targets for frustrated Lewis pair (FLP)-mediated catalysis. Unlike neutral boranes, which are the most prevalent LAs for FLP hydrogenations, the Lewis acidity of cations can be tuned through modulation of the counteranion; however, detailed studies on such anion effects are currently lacking in the literature. Herein, we present experimental and computational studies which probe the mechanism of H2 activation using iPr3SnOTf (1-OTf) in conjunction with a coordinating (quinuclidine; qui) and noncoordinating (2,4,6-collidine; col) base and compare its reactivity with {iPr3Sn·base}{Al[OC(CF3)3]4} (base = qui/col) systems which lack a coordinating anion to investigate the active species responsible for H2 activation and hence resolve any mechanistic roles for OTf– in the iPr3SnOTf-mediated pathway.

U2 - 10.1021/acscatal.0c02023

DO - 10.1021/acscatal.0c02023

M3 - Article

VL - 10

SP - 7573

EP - 7583

JO - ACS Catalysis

JF - ACS Catalysis

SN - 2155-5435

IS - 14

ER -

Establishing the Role of Triflate Anions in H2 Activation by a Cationic Triorganotin(IV) Lewis Acid

Abstract

Access to Document

Fingerprint

Cite this

Establishing the Role of Triflate Anions in H₂ Activation by a Cationic Triorganotin(IV) Lewis Acid