Organometallic reactivity patterns in fluorocarbons and implications for catalysis

Synthesis, structure, solubility, and oxidative additions of a fluorous analogue of Vaska's complex, trans-Ir(CO)(Cl)[P(CH2CH2(CF2) 5CF3)3]2

Marie Andrée Guillevic, Christian Rocaboy, Atta M. Arif, I. Horváth, J. A. Gladysz

Research output: Contribution to journalArticle

80 Citations (Scopus)

Abstract

The reaction of [Ir(Cl)(cod)]2, P(CH2CH2(CF2)5CF3) 3, and CO (1 atm) gaves the title comnound (2, 97%). Tri(n-octyl)phosphine (3) and rhodium (4) analogues are similarly prepared. Crystal structures of 2 and 4 show anti CCCC conformations m the six perfluoroalkyl groups (average torsion angle 169°), with four chains (two per phosphorus) in parallel coplanar arrays that define ca. 21 × 6 Å "rafts". The other two chains extend on a common side of the raft, which pack back-to-back in stacks, maximizing parallel chains in every dimension. DSC shows one phase transition (melting, 2/4 75/79°C) prior to thermal decomposition (> 200°C). The IR vCO values (2/3/4 1975/1942/1979 cm-1) show that the CH2-CH2 spacers do not completely insulate the metals from the perfluoroalkyl groups. Both 2 and 4 are soluble in CF3C6F11, CF3C6H5, ether, THF, and acetone but insoluble in hexane toluene, CHCl3, and CH2Cl2 (CF3C6F11/THF partition coefficient >99.7:2, and 3O2 or 1O2 in (CF3C6F11 give Ir(CO)(Cl)(R)(I)[P(CH2CH2(CF2) 5CF3)3]2 (R = CH2CH2(CF2)7 CF3 (5), CH3 (6), CH(CH3)CH2CH3 (7), 70-84%), Ir(CO)(Cl)(H)2[P(CH2CH2-(CF2) 5CF3)3]2 82%), and Ir(CO)(Cl)(O2)[P(CH2CH2(CF2) 5CF3)3]2 (9, 67%), respectively Additions of RI occur by free-radical chain mechanisms (inhibition by duroquinone; slower dark reactions; rates 7 > 5 > 6) with no evidence for polar pathways. Complex 9 forms more rapidly in THF, indicating that (relative to THF) 2 and 3O2 are stabilized by CF3C6F11 more than the transition state.

Original languageEnglish
Pages (from-to)707-717
Number of pages11
JournalOrganometallics
Volume17
Issue number4
Publication statusPublished - Feb 16 1998

Fingerprint

Fluorocarbons
fluorocarbons
Organometallics
Carbon Monoxide
Catalysis
catalysis
solubility
reactivity
Solubility
analogs
rafts
phosphine
synthesis
Rhodium
Toluene
Hexanes
Acetone
rhodium
phosphines
Ether

ASJC Scopus subject areas

  • Inorganic Chemistry
  • Organic Chemistry

Cite this

Organometallic reactivity patterns in fluorocarbons and implications for catalysis : Synthesis, structure, solubility, and oxidative additions of a fluorous analogue of Vaska's complex, trans-Ir(CO)(Cl)[P(CH2CH2(CF2) 5CF3)3]2. / Guillevic, Marie Andrée; Rocaboy, Christian; Arif, Atta M.; Horváth, I.; Gladysz, J. A.

In: Organometallics, Vol. 17, No. 4, 16.02.1998, p. 707-717.

Research output: Contribution to journalArticle

@article{7bb9a466f1db43c5a1c152264bdf55c2,
title = "Organometallic reactivity patterns in fluorocarbons and implications for catalysis: Synthesis, structure, solubility, and oxidative additions of a fluorous analogue of Vaska's complex, trans-Ir(CO)(Cl)[P(CH2CH2(CF2) 5CF3)3]2",
abstract = "The reaction of [Ir(Cl)(cod)]2, P(CH2CH2(CF2)5CF3) 3, and CO (1 atm) gaves the title comnound (2, 97{\%}). Tri(n-octyl)phosphine (3) and rhodium (4) analogues are similarly prepared. Crystal structures of 2 and 4 show anti CCCC conformations m the six perfluoroalkyl groups (average torsion angle 169°), with four chains (two per phosphorus) in parallel coplanar arrays that define ca. 21 × 6 {\AA} {"}rafts{"}. The other two chains extend on a common side of the raft, which pack back-to-back in stacks, maximizing parallel chains in every dimension. DSC shows one phase transition (melting, 2/4 75/79°C) prior to thermal decomposition (> 200°C). The IR vCO values (2/3/4 1975/1942/1979 cm-1) show that the CH2-CH2 spacers do not completely insulate the metals from the perfluoroalkyl groups. Both 2 and 4 are soluble in CF3C6F11, CF3C6H5, ether, THF, and acetone but insoluble in hexane toluene, CHCl3, and CH2Cl2 (CF3C6F11/THF partition coefficient >99.7:2, and 3O2 or 1O2 in (CF3C6F11 give Ir(CO)(Cl)(R)(I)[P(CH2CH2(CF2) 5CF3)3]2 (R = CH2CH2(CF2)7 CF3 (5), CH3 (6), CH(CH3)CH2CH3 (7), 70-84{\%}), Ir(CO)(Cl)(H)2[P(CH2CH2-(CF2) 5CF3)3]2 82{\%}), and Ir(CO)(Cl)(O2)[P(CH2CH2(CF2) 5CF3)3]2 (9, 67{\%}), respectively Additions of RI occur by free-radical chain mechanisms (inhibition by duroquinone; slower dark reactions; rates 7 > 5 > 6) with no evidence for polar pathways. Complex 9 forms more rapidly in THF, indicating that (relative to THF) 2 and 3O2 are stabilized by CF3C6F11 more than the transition state.",
author = "Guillevic, {Marie Andr{\'e}e} and Christian Rocaboy and Arif, {Atta M.} and I. Horv{\'a}th and Gladysz, {J. A.}",
year = "1998",
month = "2",
day = "16",
language = "English",
volume = "17",
pages = "707--717",
journal = "Organometallics",
issn = "0276-7333",
publisher = "American Chemical Society",
number = "4",

}

TY - JOUR

T1 - Organometallic reactivity patterns in fluorocarbons and implications for catalysis

T2 - Synthesis, structure, solubility, and oxidative additions of a fluorous analogue of Vaska's complex, trans-Ir(CO)(Cl)[P(CH2CH2(CF2) 5CF3)3]2

AU - Guillevic, Marie Andrée

AU - Rocaboy, Christian

AU - Arif, Atta M.

AU - Horváth, I.

AU - Gladysz, J. A.

PY - 1998/2/16

Y1 - 1998/2/16

N2 - The reaction of [Ir(Cl)(cod)]2, P(CH2CH2(CF2)5CF3) 3, and CO (1 atm) gaves the title comnound (2, 97%). Tri(n-octyl)phosphine (3) and rhodium (4) analogues are similarly prepared. Crystal structures of 2 and 4 show anti CCCC conformations m the six perfluoroalkyl groups (average torsion angle 169°), with four chains (two per phosphorus) in parallel coplanar arrays that define ca. 21 × 6 Å "rafts". The other two chains extend on a common side of the raft, which pack back-to-back in stacks, maximizing parallel chains in every dimension. DSC shows one phase transition (melting, 2/4 75/79°C) prior to thermal decomposition (> 200°C). The IR vCO values (2/3/4 1975/1942/1979 cm-1) show that the CH2-CH2 spacers do not completely insulate the metals from the perfluoroalkyl groups. Both 2 and 4 are soluble in CF3C6F11, CF3C6H5, ether, THF, and acetone but insoluble in hexane toluene, CHCl3, and CH2Cl2 (CF3C6F11/THF partition coefficient >99.7:2, and 3O2 or 1O2 in (CF3C6F11 give Ir(CO)(Cl)(R)(I)[P(CH2CH2(CF2) 5CF3)3]2 (R = CH2CH2(CF2)7 CF3 (5), CH3 (6), CH(CH3)CH2CH3 (7), 70-84%), Ir(CO)(Cl)(H)2[P(CH2CH2-(CF2) 5CF3)3]2 82%), and Ir(CO)(Cl)(O2)[P(CH2CH2(CF2) 5CF3)3]2 (9, 67%), respectively Additions of RI occur by free-radical chain mechanisms (inhibition by duroquinone; slower dark reactions; rates 7 > 5 > 6) with no evidence for polar pathways. Complex 9 forms more rapidly in THF, indicating that (relative to THF) 2 and 3O2 are stabilized by CF3C6F11 more than the transition state.

AB - The reaction of [Ir(Cl)(cod)]2, P(CH2CH2(CF2)5CF3) 3, and CO (1 atm) gaves the title comnound (2, 97%). Tri(n-octyl)phosphine (3) and rhodium (4) analogues are similarly prepared. Crystal structures of 2 and 4 show anti CCCC conformations m the six perfluoroalkyl groups (average torsion angle 169°), with four chains (two per phosphorus) in parallel coplanar arrays that define ca. 21 × 6 Å "rafts". The other two chains extend on a common side of the raft, which pack back-to-back in stacks, maximizing parallel chains in every dimension. DSC shows one phase transition (melting, 2/4 75/79°C) prior to thermal decomposition (> 200°C). The IR vCO values (2/3/4 1975/1942/1979 cm-1) show that the CH2-CH2 spacers do not completely insulate the metals from the perfluoroalkyl groups. Both 2 and 4 are soluble in CF3C6F11, CF3C6H5, ether, THF, and acetone but insoluble in hexane toluene, CHCl3, and CH2Cl2 (CF3C6F11/THF partition coefficient >99.7:2, and 3O2 or 1O2 in (CF3C6F11 give Ir(CO)(Cl)(R)(I)[P(CH2CH2(CF2) 5CF3)3]2 (R = CH2CH2(CF2)7 CF3 (5), CH3 (6), CH(CH3)CH2CH3 (7), 70-84%), Ir(CO)(Cl)(H)2[P(CH2CH2-(CF2) 5CF3)3]2 82%), and Ir(CO)(Cl)(O2)[P(CH2CH2(CF2) 5CF3)3]2 (9, 67%), respectively Additions of RI occur by free-radical chain mechanisms (inhibition by duroquinone; slower dark reactions; rates 7 > 5 > 6) with no evidence for polar pathways. Complex 9 forms more rapidly in THF, indicating that (relative to THF) 2 and 3O2 are stabilized by CF3C6F11 more than the transition state.

UR - http://www.scopus.com/inward/record.url?scp=0000961372&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=0000961372&partnerID=8YFLogxK

M3 - Article

VL - 17

SP - 707

EP - 717

JO - Organometallics

JF - Organometallics

SN - 0276-7333

IS - 4

ER -