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

Cybulski, M.K., Riddlestone, Ian M., Mahon, M.F., Woodman, T.J. and Whittlesey, M.K. (2015) Stoichiometric and catalytic C-F bond activation by the trans-dihydride NHC complex [Ru(IEt2Me2)2-(PPh3)2H2] (IEt2Me2 = 1,3-diethyl-4,5-dimethylimidazol-2-ylidene) Dalton Transactions, 44 (45). pp. 19597-19605.

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Abstract

The room temperature reaction of C6F6 or C6F5H with [Ru(IEt2Me2)2(PPh3)2H2] (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 C6F6via 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.

Item Type: Article
Divisions : Faculty of Engineering and Physical Sciences > Chemistry
Authors :
NameEmailORCID
Cybulski, M.K.
Riddlestone, Ian M.i.riddlestone@surrey.ac.uk
Mahon, M.F.
Woodman, T.J.
Whittlesey, M.K.
Date : 7 December 2015
DOI : 10.1039/c5dt01996f
Depositing User : Clive Harris
Date Deposited : 24 Jun 2019 10:52
Last Modified : 06 Jul 2019 05:27
URI: http://epubs.surrey.ac.uk/id/eprint/852019

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