2-[Bis(diphenylphosphino)methyl]pyridine (PNP) derivatives of rhenium carbonyl. Crystal and molecular structure of Re2(μ-PPh2)(μ-η1,η 4-CHPPh2C5H4N)(CO)7

Bruce M. Mattson, Larry N. Ito

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Abstract

Two new 2-[bis(diphenylphosphino)methyl]pyridine (PNP) complexes of rhenium have been synthesized. Re222-PNP)(CO)8 was synthesized from Re2(CO)8(μ-H)(μ-CH=CHC4H9) and an excess of PNP in CH2Cl2 solution. Re222-PNP)(CO)8 was characterized by IR, mass, and 1H, 31P, and 13C NMR spectroscopies. The structure of Re222-PNP)(CO)8 is based on Re2(CO)10 in which one eq-CO on each Re has been replaced with phosphino groups from the bridging PNP ligand. The pyridyl group is not coordinated. Re222-PNP)(CO)8 thermally decarbonylates in toluene solution to afford Re2(μ-PPh2)(μ-η14-CHPPh2C6H4N)(CO)7 in high yield. Re2(μ-PPh2)(μ-η14-CHPPh2C5H4N)(CO)7 was characterized spectroscopically and by a single-crystal X-ray diffraction [P, a = 10.906 (10) Å, b = 18.164 (9) Å, c = 10.973 (6) Å, α = 98.56 (5)°, β = 119.12 (6)°, γ = 94.14 (8)°, Z = 2, D = 1.951 g cm-3, R = 0.045]. The molecular structure was found to consist of two octahedral rhenium centers joined by a μ-PPh2 ligand and a μ-C5H4NCHPPh2 (PN) moiety. These two bridges are the fragments that result when the coordinated PNP in Re222-PNP)(CO)8 undergoes P-C bond activation. The PN group chelates in a bidentate manner to one Re and is σ-bonded via the methine C to the other Re. No Re-Re bond exists (4.189 Å).

Original languageEnglish
Pages (from-to)391-395
Number of pages5
JournalOrganometallics
Volume8
Issue number2
StatePublished - 1989

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Rhenium
rhenium
Carbon Monoxide
Molecular structure
pyridines
molecular structure
Crystal structure
Derivatives
crystal structure
pyridine
Ligands
ligands
chelates
Toluene
toluene
Nuclear magnetic resonance spectroscopy
fragments
activation
methylidyne
Chemical activation

All Science Journal Classification (ASJC) codes

  • Inorganic Chemistry
  • Organic Chemistry

Cite this

@article{e73196a89d6848f19b7c3aa7731b1c23,
title = "2-[Bis(diphenylphosphino)methyl]pyridine (PNP) derivatives of rhenium carbonyl. Crystal and molecular structure of Re2(μ-PPh2)(μ-η1,η 4-CHPPh2C5H4N)(CO)7",
abstract = "Two new 2-[bis(diphenylphosphino)methyl]pyridine (PNP) complexes of rhenium have been synthesized. Re2(η2,η2-PNP)(CO)8 was synthesized from Re2(CO)8(μ-H)(μ-CH=CHC4H9) and an excess of PNP in CH2Cl2 solution. Re2(η2,η2-PNP)(CO)8 was characterized by IR, mass, and 1H, 31P, and 13C NMR spectroscopies. The structure of Re2(η2,η2-PNP)(CO)8 is based on Re2(CO)10 in which one eq-CO on each Re has been replaced with phosphino groups from the bridging PNP ligand. The pyridyl group is not coordinated. Re2(η2,η2-PNP)(CO)8 thermally decarbonylates in toluene solution to afford Re2(μ-PPh2)(μ-η1,η 4-CHPPh2C6H4N)(CO)7 in high yield. Re2(μ-PPh2)(μ-η1,η 4-CHPPh2C5H4N)(CO)7 was characterized spectroscopically and by a single-crystal X-ray diffraction [P, a = 10.906 (10) {\AA}, b = 18.164 (9) {\AA}, c = 10.973 (6) {\AA}, α = 98.56 (5)°, β = 119.12 (6)°, γ = 94.14 (8)°, Z = 2, D = 1.951 g cm-3, R = 0.045]. The molecular structure was found to consist of two octahedral rhenium centers joined by a μ-PPh2 ligand and a μ-C5H4NCHPPh2 (PN) moiety. These two bridges are the fragments that result when the coordinated PNP in Re2(η2,η2-PNP)(CO)8 undergoes P-C bond activation. The PN group chelates in a bidentate manner to one Re and is σ-bonded via the methine C to the other Re. No Re-Re bond exists (4.189 {\AA}).",
author = "Mattson, {Bruce M.} and Ito, {Larry N.}",
year = "1989",
language = "English",
volume = "8",
pages = "391--395",
journal = "Organometallics",
issn = "0276-7333",
publisher = "American Chemical Society",
number = "2",

}

TY - JOUR

T1 - 2-[Bis(diphenylphosphino)methyl]pyridine (PNP) derivatives of rhenium carbonyl. Crystal and molecular structure of Re2(μ-PPh2)(μ-η1,η 4-CHPPh2C5H4N)(CO)7

AU - Mattson, Bruce M.

AU - Ito, Larry N.

PY - 1989

Y1 - 1989

N2 - Two new 2-[bis(diphenylphosphino)methyl]pyridine (PNP) complexes of rhenium have been synthesized. Re2(η2,η2-PNP)(CO)8 was synthesized from Re2(CO)8(μ-H)(μ-CH=CHC4H9) and an excess of PNP in CH2Cl2 solution. Re2(η2,η2-PNP)(CO)8 was characterized by IR, mass, and 1H, 31P, and 13C NMR spectroscopies. The structure of Re2(η2,η2-PNP)(CO)8 is based on Re2(CO)10 in which one eq-CO on each Re has been replaced with phosphino groups from the bridging PNP ligand. The pyridyl group is not coordinated. Re2(η2,η2-PNP)(CO)8 thermally decarbonylates in toluene solution to afford Re2(μ-PPh2)(μ-η1,η 4-CHPPh2C6H4N)(CO)7 in high yield. Re2(μ-PPh2)(μ-η1,η 4-CHPPh2C5H4N)(CO)7 was characterized spectroscopically and by a single-crystal X-ray diffraction [P, a = 10.906 (10) Å, b = 18.164 (9) Å, c = 10.973 (6) Å, α = 98.56 (5)°, β = 119.12 (6)°, γ = 94.14 (8)°, Z = 2, D = 1.951 g cm-3, R = 0.045]. The molecular structure was found to consist of two octahedral rhenium centers joined by a μ-PPh2 ligand and a μ-C5H4NCHPPh2 (PN) moiety. These two bridges are the fragments that result when the coordinated PNP in Re2(η2,η2-PNP)(CO)8 undergoes P-C bond activation. The PN group chelates in a bidentate manner to one Re and is σ-bonded via the methine C to the other Re. No Re-Re bond exists (4.189 Å).

AB - Two new 2-[bis(diphenylphosphino)methyl]pyridine (PNP) complexes of rhenium have been synthesized. Re2(η2,η2-PNP)(CO)8 was synthesized from Re2(CO)8(μ-H)(μ-CH=CHC4H9) and an excess of PNP in CH2Cl2 solution. Re2(η2,η2-PNP)(CO)8 was characterized by IR, mass, and 1H, 31P, and 13C NMR spectroscopies. The structure of Re2(η2,η2-PNP)(CO)8 is based on Re2(CO)10 in which one eq-CO on each Re has been replaced with phosphino groups from the bridging PNP ligand. The pyridyl group is not coordinated. Re2(η2,η2-PNP)(CO)8 thermally decarbonylates in toluene solution to afford Re2(μ-PPh2)(μ-η1,η 4-CHPPh2C6H4N)(CO)7 in high yield. Re2(μ-PPh2)(μ-η1,η 4-CHPPh2C5H4N)(CO)7 was characterized spectroscopically and by a single-crystal X-ray diffraction [P, a = 10.906 (10) Å, b = 18.164 (9) Å, c = 10.973 (6) Å, α = 98.56 (5)°, β = 119.12 (6)°, γ = 94.14 (8)°, Z = 2, D = 1.951 g cm-3, R = 0.045]. The molecular structure was found to consist of two octahedral rhenium centers joined by a μ-PPh2 ligand and a μ-C5H4NCHPPh2 (PN) moiety. These two bridges are the fragments that result when the coordinated PNP in Re2(η2,η2-PNP)(CO)8 undergoes P-C bond activation. The PN group chelates in a bidentate manner to one Re and is σ-bonded via the methine C to the other Re. No Re-Re bond exists (4.189 Å).

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