Stoichiometric and catalytic C-F bond activation by the trans-dihydride complex [Ru(IEt2Me2)2(PPh3)2H2] (IEt2Me2 = 1,3-diethyl-4,5-dimethylimidazol-2-ylidene)

Mateusz K. Cybulski, Ian M. Riddlestone, Mary F. Mahon, Timothy J. Woodman, Michael K. Whittlesey

Research output: Contribution to journalArticle

11 Citations (Scopus)
75 Downloads (Pure)

Abstract

The room temperature reaction of C6F6 or C6F5H with [Ru(IEt2Me2)2(PPh3)2H¬2] (1; IEt2Me2 = 1,3-diethyl-4,5-dimethylimidazol-2-ylidene) generated a mixture of the trans-hydride fluoride complex [Ru(IEt2Me2)2(PPh3)2HF] (2) and the bis-carbene pentafluorophenyl species [Ru(IEt2Me2)2(PPh3)(C6F5)H] (3). The formation of 3 resulted from C-H activation of C6F5H (formed from C6F6 via stoichiometric hydrodefluorination), a process which could be reversed by working under 4 atm H2. Upon heating 1 with C6F5H, the bis-phosphine derivative [Ru(IEt2Me2)(PPh3)2(C6F5)H] (4) was isolated. A more efficient route to 2 involved treatment of 1 with 0.33 eq of TREAT-HF (Et3N·3HF); excess reagent gave instead the [H2F3]- salt (5) of the known cation [Ru(IEt2Me2)2(PPh3)2H]+. Under catalytic conditions, 1 proved to be an active precursor for hydrodefluorination, converting C6F6 to a mixture of tri, di and monofluorobenzenes (TON = 37) at 363 K with 10 mol% 1 and Et3SiH as the reductant.
Original languageEnglish
Pages (from-to)19597-19605
Number of pages9
JournalDalton Transactions
Volume44
Issue number45
Early online date17 Jul 2015
DOIs
Publication statusPublished - 2015

Fingerprint

phosphine
Chemical activation
Reducing Agents
Fluorides
Hydrides
Cations
Salts
Derivatives
Heating
Temperature
carbene

Cite this

@article{f590e17e2694422a887744656cef4f17,
title = "Stoichiometric and catalytic C-F bond activation by the trans-dihydride complex [Ru(IEt2Me2)2(PPh3)2H2] (IEt2Me2 = 1,3-diethyl-4,5-dimethylimidazol-2-ylidene)",
abstract = "The room temperature reaction of C6F6 or C6F5H with [Ru(IEt2Me2)2(PPh3)2H¬2] (1; IEt2Me2 = 1,3-diethyl-4,5-dimethylimidazol-2-ylidene) generated a mixture of the trans-hydride fluoride complex [Ru(IEt2Me2)2(PPh3)2HF] (2) and the bis-carbene pentafluorophenyl species [Ru(IEt2Me2)2(PPh3)(C6F5)H] (3). The formation of 3 resulted from C-H activation of C6F5H (formed from C6F6 via stoichiometric hydrodefluorination), a process which could be reversed by working under 4 atm H2. Upon heating 1 with C6F5H, the bis-phosphine derivative [Ru(IEt2Me2)(PPh3)2(C6F5)H] (4) was isolated. A more efficient route to 2 involved treatment of 1 with 0.33 eq of TREAT-HF (Et3N·3HF); excess reagent gave instead the [H2F3]- salt (5) of the known cation [Ru(IEt2Me2)2(PPh3)2H]+. Under catalytic conditions, 1 proved to be an active precursor for hydrodefluorination, converting C6F6 to a mixture of tri, di and monofluorobenzenes (TON = 37) at 363 K with 10 mol{\%} 1 and Et3SiH as the reductant.",
author = "Cybulski, {Mateusz K.} and Riddlestone, {Ian M.} and Mahon, {Mary F.} and Woodman, {Timothy J.} and Whittlesey, {Michael K.}",
year = "2015",
doi = "10.1039/C5DT01996F",
language = "English",
volume = "44",
pages = "19597--19605",
journal = "Dalton Transactions",
issn = "1477-9226",
publisher = "Royal Society of Chemistry",
number = "45",

}

TY - JOUR

T1 - Stoichiometric and catalytic C-F bond activation by the trans-dihydride complex [Ru(IEt2Me2)2(PPh3)2H2] (IEt2Me2 = 1,3-diethyl-4,5-dimethylimidazol-2-ylidene)

AU - Cybulski, Mateusz K.

AU - Riddlestone, Ian M.

AU - Mahon, Mary F.

AU - Woodman, Timothy J.

AU - Whittlesey, Michael K.

PY - 2015

Y1 - 2015

N2 - The room temperature reaction of C6F6 or C6F5H with [Ru(IEt2Me2)2(PPh3)2H¬2] (1; IEt2Me2 = 1,3-diethyl-4,5-dimethylimidazol-2-ylidene) generated a mixture of the trans-hydride fluoride complex [Ru(IEt2Me2)2(PPh3)2HF] (2) and the bis-carbene pentafluorophenyl species [Ru(IEt2Me2)2(PPh3)(C6F5)H] (3). The formation of 3 resulted from C-H activation of C6F5H (formed from C6F6 via stoichiometric hydrodefluorination), a process which could be reversed by working under 4 atm H2. Upon heating 1 with C6F5H, the bis-phosphine derivative [Ru(IEt2Me2)(PPh3)2(C6F5)H] (4) was isolated. A more efficient route to 2 involved treatment of 1 with 0.33 eq of TREAT-HF (Et3N·3HF); excess reagent gave instead the [H2F3]- salt (5) of the known cation [Ru(IEt2Me2)2(PPh3)2H]+. Under catalytic conditions, 1 proved to be an active precursor for hydrodefluorination, converting C6F6 to a mixture of tri, di and monofluorobenzenes (TON = 37) at 363 K with 10 mol% 1 and Et3SiH as the reductant.

AB - The room temperature reaction of C6F6 or C6F5H with [Ru(IEt2Me2)2(PPh3)2H¬2] (1; IEt2Me2 = 1,3-diethyl-4,5-dimethylimidazol-2-ylidene) generated a mixture of the trans-hydride fluoride complex [Ru(IEt2Me2)2(PPh3)2HF] (2) and the bis-carbene pentafluorophenyl species [Ru(IEt2Me2)2(PPh3)(C6F5)H] (3). The formation of 3 resulted from C-H activation of C6F5H (formed from C6F6 via stoichiometric hydrodefluorination), a process which could be reversed by working under 4 atm H2. Upon heating 1 with C6F5H, the bis-phosphine derivative [Ru(IEt2Me2)(PPh3)2(C6F5)H] (4) was isolated. A more efficient route to 2 involved treatment of 1 with 0.33 eq of TREAT-HF (Et3N·3HF); excess reagent gave instead the [H2F3]- salt (5) of the known cation [Ru(IEt2Me2)2(PPh3)2H]+. Under catalytic conditions, 1 proved to be an active precursor for hydrodefluorination, converting C6F6 to a mixture of tri, di and monofluorobenzenes (TON = 37) at 363 K with 10 mol% 1 and Et3SiH as the reductant.

UR - http://dx.doi.org/10.1039/C5DT01996F

U2 - 10.1039/C5DT01996F

DO - 10.1039/C5DT01996F

M3 - Article

VL - 44

SP - 19597

EP - 19605

JO - Dalton Transactions

JF - Dalton Transactions

SN - 1477-9226

IS - 45

ER -