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

Research output: Contribution to journalArticle

2 Citations (Scopus)
13 Downloads (Pure)

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).
Original languageEnglish
Pages (from-to)13749-13760
Number of pages12
JournalInorganic Chemistry
Volume57
Issue number21
Early online date10 Oct 2018
DOIs
Publication statusPublished - 5 Nov 2018

Fingerprint

dihydrides
Ruthenium
Fluorides
ruthenium
halides
isolation
Substitution reactions
reactivity
Chemical activation
activation
Ligands
products
fluorides
cleavage
substitutes
ligands

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry
  • Inorganic Chemistry

Cite this

@article{958b67e733364de38dd753230aef758a,
title = "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",
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).",
author = "Mateusz Cybulski and Caroline Davies and John Lowe and Mary Mahon and Michael Whittlesey",
year = "2018",
month = "11",
day = "5",
doi = "10.1021/acs.inorgchem.8b02286",
language = "English",
volume = "57",
pages = "13749--13760",
journal = "Inorganic Chemistry",
issn = "0020-1669",
publisher = "American Chemical Society",
number = "21",

}

TY - JOUR

T1 - 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

AU - Cybulski, Mateusz

AU - Davies, Caroline

AU - Lowe, John

AU - Mahon, Mary

AU - Whittlesey, Michael

PY - 2018/11/5

Y1 - 2018/11/5

N2 - 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).

AB - 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).

UR - http://www.scopus.com/inward/record.url?scp=85054853167&partnerID=8YFLogxK

U2 - 10.1021/acs.inorgchem.8b02286

DO - 10.1021/acs.inorgchem.8b02286

M3 - Article

VL - 57

SP - 13749

EP - 13760

JO - Inorganic Chemistry

JF - Inorganic Chemistry

SN - 0020-1669

IS - 21

ER -