Syntheses and carbonyliridium complexes of unsymmetrically substituted fluorous trialkylphosphanes: Precision tuning of electronic properties, including insulation of the perfluoroalkyl groups

Luke J. Alvey, Ralf Meier, T. Soós, Paul Bernatis, John A. Gladysz

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80 Citations (Scopus)

Abstract

Reactions of iodides I(CH2)(m)R(f8) [m = 2-4; R(f8) = (CF2)7CF3] and LiPH2 · DME (-45 °C, THF) give the primary phosphanes PH2(CH2)(m)R(f8) (7-9; 48-76%). Radical-initiated reactions (100 °C) of 7 and H2C=CHCH2R(f8), 8 and H2C=CHR(f8) or H2C= CHCH2CH2R(f8), and 9 and H2C=CHCH2R(f8), give the title phosphanes P[(CH2)(m)R(f8)]2[(CH2)(m')R(f8)] [m/m' = 2/3 (10), 3/2 (11), 3/4 (12), 4/3 (13); 70-76%]. The symmetrically substituted phosphane P[(CH2)(m)R(f8)]3 (m = 5, 6) is similarly prepared from PH3 and H2C=CHCH2CH2CH2R(f8), analogously to previously reported homologs [m = 2 (2), 3 (4), 4 (5)]. Reactions of 10-13 and 2, 4, 5, and 6 with [Ir(COD)Cl]2 and CO give trans-Ir(CO)(Cl)(PR2R')2 (70-83%). The IR V(CO) values show a monotonic decrease with increasing numbers of CH2 groups. Phosphanes 13, 5, and 6 have the most CH2 groups, and give V(CO) values 10, 7, and 4 cm-1 higher than the unfluorinated phosphane P[(CH2)7CH3]3. Hence, 6 provides nearly complete insulation of the iridium center from the electronegative perfluoroalkyl groups. Analogous rhodium derivatives of 4 and 5 are also described.

Original languageEnglish
Pages (from-to)1975-1983
Number of pages9
JournalEuropean Journal of Inorganic Chemistry
Issue number9
Publication statusPublished - 2000

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phosphine
Electronic properties
Insulation
Carbon Monoxide
Tuning
Iridium
Rhodium
Iodides
Derivatives

Keywords

  • Carbonyl complexes
  • Donor-acceptor systems
  • Fluorine
  • Iridium
  • Phosphanes

ASJC Scopus subject areas

  • Inorganic Chemistry

Cite this

@article{f0a6380c30d24341a70b1a61e5ff24f3,
title = "Syntheses and carbonyliridium complexes of unsymmetrically substituted fluorous trialkylphosphanes: Precision tuning of electronic properties, including insulation of the perfluoroalkyl groups",
abstract = "Reactions of iodides I(CH2)(m)R(f8) [m = 2-4; R(f8) = (CF2)7CF3] and LiPH2 · DME (-45 °C, THF) give the primary phosphanes PH2(CH2)(m)R(f8) (7-9; 48-76{\%}). Radical-initiated reactions (100 °C) of 7 and H2C=CHCH2R(f8), 8 and H2C=CHR(f8) or H2C= CHCH2CH2R(f8), and 9 and H2C=CHCH2R(f8), give the title phosphanes P[(CH2)(m)R(f8)]2[(CH2)(m')R(f8)] [m/m' = 2/3 (10), 3/2 (11), 3/4 (12), 4/3 (13); 70-76{\%}]. The symmetrically substituted phosphane P[(CH2)(m)R(f8)]3 (m = 5, 6) is similarly prepared from PH3 and H2C=CHCH2CH2CH2R(f8), analogously to previously reported homologs [m = 2 (2), 3 (4), 4 (5)]. Reactions of 10-13 and 2, 4, 5, and 6 with [Ir(COD)Cl]2 and CO give trans-Ir(CO)(Cl)(PR2R')2 (70-83{\%}). The IR V(CO) values show a monotonic decrease with increasing numbers of CH2 groups. Phosphanes 13, 5, and 6 have the most CH2 groups, and give V(CO) values 10, 7, and 4 cm-1 higher than the unfluorinated phosphane P[(CH2)7CH3]3. Hence, 6 provides nearly complete insulation of the iridium center from the electronegative perfluoroalkyl groups. Analogous rhodium derivatives of 4 and 5 are also described.",
keywords = "Carbonyl complexes, Donor-acceptor systems, Fluorine, Iridium, Phosphanes",
author = "Alvey, {Luke J.} and Ralf Meier and T. So{\'o}s and Paul Bernatis and Gladysz, {John A.}",
year = "2000",
language = "English",
pages = "1975--1983",
journal = "Chemische Berichte",
issn = "0009-2940",
publisher = "Wiley-VCH Verlag",
number = "9",

}

TY - JOUR

T1 - Syntheses and carbonyliridium complexes of unsymmetrically substituted fluorous trialkylphosphanes

T2 - Precision tuning of electronic properties, including insulation of the perfluoroalkyl groups

AU - Alvey, Luke J.

AU - Meier, Ralf

AU - Soós, T.

AU - Bernatis, Paul

AU - Gladysz, John A.

PY - 2000

Y1 - 2000

N2 - Reactions of iodides I(CH2)(m)R(f8) [m = 2-4; R(f8) = (CF2)7CF3] and LiPH2 · DME (-45 °C, THF) give the primary phosphanes PH2(CH2)(m)R(f8) (7-9; 48-76%). Radical-initiated reactions (100 °C) of 7 and H2C=CHCH2R(f8), 8 and H2C=CHR(f8) or H2C= CHCH2CH2R(f8), and 9 and H2C=CHCH2R(f8), give the title phosphanes P[(CH2)(m)R(f8)]2[(CH2)(m')R(f8)] [m/m' = 2/3 (10), 3/2 (11), 3/4 (12), 4/3 (13); 70-76%]. The symmetrically substituted phosphane P[(CH2)(m)R(f8)]3 (m = 5, 6) is similarly prepared from PH3 and H2C=CHCH2CH2CH2R(f8), analogously to previously reported homologs [m = 2 (2), 3 (4), 4 (5)]. Reactions of 10-13 and 2, 4, 5, and 6 with [Ir(COD)Cl]2 and CO give trans-Ir(CO)(Cl)(PR2R')2 (70-83%). The IR V(CO) values show a monotonic decrease with increasing numbers of CH2 groups. Phosphanes 13, 5, and 6 have the most CH2 groups, and give V(CO) values 10, 7, and 4 cm-1 higher than the unfluorinated phosphane P[(CH2)7CH3]3. Hence, 6 provides nearly complete insulation of the iridium center from the electronegative perfluoroalkyl groups. Analogous rhodium derivatives of 4 and 5 are also described.

AB - Reactions of iodides I(CH2)(m)R(f8) [m = 2-4; R(f8) = (CF2)7CF3] and LiPH2 · DME (-45 °C, THF) give the primary phosphanes PH2(CH2)(m)R(f8) (7-9; 48-76%). Radical-initiated reactions (100 °C) of 7 and H2C=CHCH2R(f8), 8 and H2C=CHR(f8) or H2C= CHCH2CH2R(f8), and 9 and H2C=CHCH2R(f8), give the title phosphanes P[(CH2)(m)R(f8)]2[(CH2)(m')R(f8)] [m/m' = 2/3 (10), 3/2 (11), 3/4 (12), 4/3 (13); 70-76%]. The symmetrically substituted phosphane P[(CH2)(m)R(f8)]3 (m = 5, 6) is similarly prepared from PH3 and H2C=CHCH2CH2CH2R(f8), analogously to previously reported homologs [m = 2 (2), 3 (4), 4 (5)]. Reactions of 10-13 and 2, 4, 5, and 6 with [Ir(COD)Cl]2 and CO give trans-Ir(CO)(Cl)(PR2R')2 (70-83%). The IR V(CO) values show a monotonic decrease with increasing numbers of CH2 groups. Phosphanes 13, 5, and 6 have the most CH2 groups, and give V(CO) values 10, 7, and 4 cm-1 higher than the unfluorinated phosphane P[(CH2)7CH3]3. Hence, 6 provides nearly complete insulation of the iridium center from the electronegative perfluoroalkyl groups. Analogous rhodium derivatives of 4 and 5 are also described.

KW - Carbonyl complexes

KW - Donor-acceptor systems

KW - Fluorine

KW - Iridium

KW - Phosphanes

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AN - SCOPUS:0033806523

SP - 1975

EP - 1983

JO - Chemische Berichte

JF - Chemische Berichte

SN - 0009-2940

IS - 9

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