Synthesis and characterization of dinuclear palladium complexes with bridging selenide or selenoxide ligands, including X-ray characterization of anti-Pd2Cl2(μ-Se)(μ-dpmMe)2 [dpmMe = 1,1-bis(diphenylphosphino)ethane]

Gábor Besenyei, L. Párkányí, Laszlo I. Simandi, Brian R. James

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Abstract

The complexes Pd2Cl2(P-P)2, where (P-P) = μ-bis(diphenylphosphino)methane, dpm, or μ-1,1-bis(diphenylphosphino)ethane, dpmMe, react with elemental selenium to give the A-frame adducts Pd2Cl2(μ-Se)(P-P)2, which can be oxidized by t-BuOOH to the μ-SeO derivatives. Reaction of H2Se with Pd2Cl2(dpm)2 generates Pd2Cl2-n-(SeH)n(μ-Se)(dpm)2 species (n = 0-2), anti-Pd2Cl2(μ-Se)(dpmMe)2 (2d) crystallizes in the monoclinic space group P21/c with a = 11.986(2) Å, b = 24.141(2) Å, c = 18.921(2 Å), β = 106.64(1)°, V = 5243.2(11)' Å3, and Z = 4; the structure was refined against F2 to wR2 = 0.1338 (R1 = 0.0476) for 9838 reflections with I > 2σ(I), 2d is the first structurally characterized A-frame complex with anti disposition of substituents at the methylene C atoms of the diphosphine ligands. A correlation between the 77Se NMR shift measured for Pd2Cl2(μ-Se)(P-P)2 and the equilibrium constant for the reversible binding of CO by the Pd2Cl2(P-P)2 species reflects factors affecting binding at the apical site.

Original languageEnglish
Pages (from-to)6118-6123
Number of pages6
JournalInorganic Chemistry
Volume34
Issue number24
Publication statusPublished - 1995

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selenides
Methane
Equilibrium constants
Palladium
Carbon Monoxide
Selenium
ethane
palladium
Nuclear magnetic resonance
Ligands
Derivatives
X rays
Atoms
ligands
synthesis
selenium
methylene
adducts
x rays
methane

ASJC Scopus subject areas

  • Inorganic Chemistry

Cite this

@article{d383edf64e3f4ea8ae0081813444f434,
title = "Synthesis and characterization of dinuclear palladium complexes with bridging selenide or selenoxide ligands, including X-ray characterization of anti-Pd2Cl2(μ-Se)(μ-dpmMe)2 [dpmMe = 1,1-bis(diphenylphosphino)ethane]",
abstract = "The complexes Pd2Cl2(P-P)2, where (P-P) = μ-bis(diphenylphosphino)methane, dpm, or μ-1,1-bis(diphenylphosphino)ethane, dpmMe, react with elemental selenium to give the A-frame adducts Pd2Cl2(μ-Se)(P-P)2, which can be oxidized by t-BuOOH to the μ-SeO derivatives. Reaction of H2Se with Pd2Cl2(dpm)2 generates Pd2Cl2-n-(SeH)n(μ-Se)(dpm)2 species (n = 0-2), anti-Pd2Cl2(μ-Se)(dpmMe)2 (2d) crystallizes in the monoclinic space group P21/c with a = 11.986(2) {\AA}, b = 24.141(2) {\AA}, c = 18.921(2 {\AA}), β = 106.64(1)°, V = 5243.2(11)' {\AA}3, and Z = 4; the structure was refined against F2 to wR2 = 0.1338 (R1 = 0.0476) for 9838 reflections with I > 2σ(I), 2d is the first structurally characterized A-frame complex with anti disposition of substituents at the methylene C atoms of the diphosphine ligands. A correlation between the 77Se NMR shift measured for Pd2Cl2(μ-Se)(P-P)2 and the equilibrium constant for the reversible binding of CO by the Pd2Cl2(P-P)2 species reflects factors affecting binding at the apical site.",
author = "G{\'a}bor Besenyei and L. P{\'a}rk{\'a}ny{\'i} and Simandi, {Laszlo I.} and James, {Brian R.}",
year = "1995",
language = "English",
volume = "34",
pages = "6118--6123",
journal = "Inorganic Chemistry",
issn = "0020-1669",
publisher = "American Chemical Society",
number = "24",

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TY - JOUR

T1 - Synthesis and characterization of dinuclear palladium complexes with bridging selenide or selenoxide ligands, including X-ray characterization of anti-Pd2Cl2(μ-Se)(μ-dpmMe)2 [dpmMe = 1,1-bis(diphenylphosphino)ethane]

AU - Besenyei, Gábor

AU - Párkányí, L.

AU - Simandi, Laszlo I.

AU - James, Brian R.

PY - 1995

Y1 - 1995

N2 - The complexes Pd2Cl2(P-P)2, where (P-P) = μ-bis(diphenylphosphino)methane, dpm, or μ-1,1-bis(diphenylphosphino)ethane, dpmMe, react with elemental selenium to give the A-frame adducts Pd2Cl2(μ-Se)(P-P)2, which can be oxidized by t-BuOOH to the μ-SeO derivatives. Reaction of H2Se with Pd2Cl2(dpm)2 generates Pd2Cl2-n-(SeH)n(μ-Se)(dpm)2 species (n = 0-2), anti-Pd2Cl2(μ-Se)(dpmMe)2 (2d) crystallizes in the monoclinic space group P21/c with a = 11.986(2) Å, b = 24.141(2) Å, c = 18.921(2 Å), β = 106.64(1)°, V = 5243.2(11)' Å3, and Z = 4; the structure was refined against F2 to wR2 = 0.1338 (R1 = 0.0476) for 9838 reflections with I > 2σ(I), 2d is the first structurally characterized A-frame complex with anti disposition of substituents at the methylene C atoms of the diphosphine ligands. A correlation between the 77Se NMR shift measured for Pd2Cl2(μ-Se)(P-P)2 and the equilibrium constant for the reversible binding of CO by the Pd2Cl2(P-P)2 species reflects factors affecting binding at the apical site.

AB - The complexes Pd2Cl2(P-P)2, where (P-P) = μ-bis(diphenylphosphino)methane, dpm, or μ-1,1-bis(diphenylphosphino)ethane, dpmMe, react with elemental selenium to give the A-frame adducts Pd2Cl2(μ-Se)(P-P)2, which can be oxidized by t-BuOOH to the μ-SeO derivatives. Reaction of H2Se with Pd2Cl2(dpm)2 generates Pd2Cl2-n-(SeH)n(μ-Se)(dpm)2 species (n = 0-2), anti-Pd2Cl2(μ-Se)(dpmMe)2 (2d) crystallizes in the monoclinic space group P21/c with a = 11.986(2) Å, b = 24.141(2) Å, c = 18.921(2 Å), β = 106.64(1)°, V = 5243.2(11)' Å3, and Z = 4; the structure was refined against F2 to wR2 = 0.1338 (R1 = 0.0476) for 9838 reflections with I > 2σ(I), 2d is the first structurally characterized A-frame complex with anti disposition of substituents at the methylene C atoms of the diphosphine ligands. A correlation between the 77Se NMR shift measured for Pd2Cl2(μ-Se)(P-P)2 and the equilibrium constant for the reversible binding of CO by the Pd2Cl2(P-P)2 species reflects factors affecting binding at the apical site.

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VL - 34

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