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

Mateusz Cybulski, Caroline Davies, John Lowe, Mary Mahon, Michael Whittlesey

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4 Citations (Scopus)
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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).
Original languageEnglish
Pages (from-to)13749-13760
Number of pages12
JournalInorganic Chemistry
Issue number21
Early online date10 Oct 2018
Publication statusPublished - 5 Nov 2018

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry
  • Inorganic Chemistry

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