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Abstract
The major product of the reaction between Ru(IMe4)2(PPh3)2H2 (1; IMe4 = 1,3,4,5-tetramethylimidazol-2-ylidene) and P(C6F5)3 (PCF) is the 5-coordinate complex
Ru(IMe4)2(PF2{C6F5})(C6F5)H 2, which is formed via a complex series of C−F/P−C bond cleavage and P−F bond formation steps. In contrast, hydrodefluorination of all six ortho C−F bonds in PCF occurs with Ru(PPh3)4H2 to afford Ru(PPh3)3HF 3. NaBArF4 abstracted the fluoride ligand in 3 to give [Ru({η6-C6H5}PPh2)(PPh3)2H][BArF4], while B2pin2 reacted with 3 in C6D6 to yield a mixture of [Ru({η6-C6D6)(PPh3)2H]+ and Ru(PPh3)4H2. Treatment of 3 with HBpin (5 equiv) and HSiR3 (R = Et, Ph; 2 equiv)
afforded Ru(PPh3)3(σ-HBpin)H2 and Ru(PPh3)3(SiR3)3H3 respectively. No stable substitution products were generated when 3 was reacted with Me3SiX (X = CF3, C6F5).
Ru(IMe4)2(PF2{C6F5})(C6F5)H 2, which is formed via a complex series of C−F/P−C bond cleavage and P−F bond formation steps. In contrast, hydrodefluorination of all six ortho C−F bonds in PCF occurs with Ru(PPh3)4H2 to afford Ru(PPh3)3HF 3. NaBArF4 abstracted the fluoride ligand in 3 to give [Ru({η6-C6H5}PPh2)(PPh3)2H][BArF4], while B2pin2 reacted with 3 in C6D6 to yield a mixture of [Ru({η6-C6D6)(PPh3)2H]+ and Ru(PPh3)4H2. Treatment of 3 with HBpin (5 equiv) and HSiR3 (R = Et, Ph; 2 equiv)
afforded Ru(PPh3)3(σ-HBpin)H2 and Ru(PPh3)3(SiR3)3H3 respectively. No stable substitution products were generated when 3 was reacted with Me3SiX (X = CF3, C6F5).
Original language | English |
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Pages (from-to) | 13749-13760 |
Number of pages | 12 |
Journal | Inorganic Chemistry |
Volume | 57 |
Issue number | 21 |
Early online date | 10 Oct 2018 |
DOIs | |
Publication status | Published - 5 Nov 2018 |
ASJC Scopus subject areas
- Physical and Theoretical Chemistry
- Inorganic Chemistry
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Dive into the research topics of 'C-F Bond Activation of P(C6F5)3 By Ruthenium Dihydride Complexes: Isolation and Reactivity of the ‘Missing’ Ru(PPh3)3H(halide) Complex, Ru(PPh3)3HF'. Together they form a unique fingerprint.Projects
- 1 Finished
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Multi N-Heterocyclic Carbene Complexes of Ruthenium for the Coordination and Reactivity of Small Molecules
Whittlesey, M. (PI)
Engineering and Physical Sciences Research Council
4/10/10 → 3/04/14
Project: Research council