Synthesis and characterisation of mono-acetylide and unsymmetrical bis-acetylide complexes of ruthenium and osmium

X-ray structure determinations on [(dppe)2Ru(Cl)(C≡C-C6H4-p-NO 2)], [(dppe)2Ru(Cl)(C≡C-C6H3-o-CH 3-p-NO2)]

Muhammad Younus, Nicholas J. Long, Paul R. Raithby, Jack Lewis, Nicola A. Page, Andrew J P White, David J. Williams, Michael C B Colbert, Andrew J. Hodge, Muhammad S. Khan, David G. Parker

Research output: Contribution to journalArticle

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Abstract

The synthesis of a series of metal mono-acetylides trans-[(dppe)2Ru(Cl)(C≡C-R)] (R = C6H4-p-C6H5, C6H4-p-CH3, C6H4-p-NO2, C6H3-o-CH3-p-NO2, dppe = Ph2PCH2CH2PPh2), and unsymmetrical metal bis-acetylides trans-[(dppm)2M(C≡C-R)(C≡C-R′)]; (M = Ru, Os; R = C6H4-p-NO2, R′ = C6H5, C6H4-p-CH3; R = C6H5, R′ = C6H4-p-C6H3) using a variety of σ-acetylide coupling reactions is reported. Three compounds have been structurally characterised, including the unsymmetrical trans-[(dppm)2Os(C≡C-R)(C≡C-R′)] (R = C6H4-p-CH3, R′ = C6H4-p-NO2] which shows the 'rigid-rod' nature of the acetylide-metal-acetylide linkage. The electrochemistry of symmetrical and unsymmetrical Ru(II) complexes demonstrates the role of the acetylide and the auxiliary ligands in determining the ease of oxidation at the metal centre whilst UV-vis spectral changes illustrate the influence of electron-withdrawing and -donating ligands.

Original languageEnglish
Pages (from-to)198-209
Number of pages12
JournalJournal of Organometallic Chemistry
Volume578
Issue number1-2
Publication statusPublished - Apr 22 1999

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Osmium
Ruthenium
osmium
ruthenium
Metals
X-Rays
methylidyne
X rays
synthesis
metals
x rays
Ligands
Electrochemistry
ligands
electrochemistry
linkages
rods
Electrons
Oxidation
oxidation

Keywords

  • Acetylide
  • Electrochemistry
  • Osmium
  • Ruthenium

ASJC Scopus subject areas

  • Biochemistry
  • Inorganic Chemistry
  • Organic Chemistry
  • Physical and Theoretical Chemistry
  • Materials Chemistry

Cite this

Synthesis and characterisation of mono-acetylide and unsymmetrical bis-acetylide complexes of ruthenium and osmium : X-ray structure determinations on [(dppe)2Ru(Cl)(C≡C-C6H4-p-NO 2)], [(dppe)2Ru(Cl)(C≡C-C6H3-o-CH 3-p-NO2)]. / Younus, Muhammad; Long, Nicholas J.; Raithby, Paul R.; Lewis, Jack; Page, Nicola A.; White, Andrew J P; Williams, David J.; Colbert, Michael C B; Hodge, Andrew J.; Khan, Muhammad S.; Parker, David G.

In: Journal of Organometallic Chemistry, Vol. 578, No. 1-2, 22.04.1999, p. 198-209.

Research output: Contribution to journalArticle

Younus, Muhammad ; Long, Nicholas J. ; Raithby, Paul R. ; Lewis, Jack ; Page, Nicola A. ; White, Andrew J P ; Williams, David J. ; Colbert, Michael C B ; Hodge, Andrew J. ; Khan, Muhammad S. ; Parker, David G. / Synthesis and characterisation of mono-acetylide and unsymmetrical bis-acetylide complexes of ruthenium and osmium : X-ray structure determinations on [(dppe)2Ru(Cl)(C≡C-C6H4-p-NO 2)], [(dppe)2Ru(Cl)(C≡C-C6H3-o-CH 3-p-NO2)]. In: Journal of Organometallic Chemistry. 1999 ; Vol. 578, No. 1-2. pp. 198-209.
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abstract = "The synthesis of a series of metal mono-acetylides trans-[(dppe)2Ru(Cl)(C≡C-R)] (R = C6H4-p-C6H5, C6H4-p-CH3, C6H4-p-NO2, C6H3-o-CH3-p-NO2, dppe = Ph2PCH2CH2PPh2), and unsymmetrical metal bis-acetylides trans-[(dppm)2M(C≡C-R)(C≡C-R′)]; (M = Ru, Os; R = C6H4-p-NO2, R′ = C6H5, C6H4-p-CH3; R = C6H5, R′ = C6H4-p-C6H3) using a variety of σ-acetylide coupling reactions is reported. Three compounds have been structurally characterised, including the unsymmetrical trans-[(dppm)2Os(C≡C-R)(C≡C-R′)] (R = C6H4-p-CH3, R′ = C6H4-p-NO2] which shows the 'rigid-rod' nature of the acetylide-metal-acetylide linkage. The electrochemistry of symmetrical and unsymmetrical Ru(II) complexes demonstrates the role of the acetylide and the auxiliary ligands in determining the ease of oxidation at the metal centre whilst UV-vis spectral changes illustrate the influence of electron-withdrawing and -donating ligands.",
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T2 - X-ray structure determinations on [(dppe)2Ru(Cl)(C≡C-C6H4-p-NO 2)], [(dppe)2Ru(Cl)(C≡C-C6H3-o-CH 3-p-NO2)]

AU - Younus, Muhammad

AU - Long, Nicholas J.

AU - Raithby, Paul R.

AU - Lewis, Jack

AU - Page, Nicola A.

AU - White, Andrew J P

AU - Williams, David J.

AU - Colbert, Michael C B

AU - Hodge, Andrew J.

AU - Khan, Muhammad S.

AU - Parker, David G.

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N2 - The synthesis of a series of metal mono-acetylides trans-[(dppe)2Ru(Cl)(C≡C-R)] (R = C6H4-p-C6H5, C6H4-p-CH3, C6H4-p-NO2, C6H3-o-CH3-p-NO2, dppe = Ph2PCH2CH2PPh2), and unsymmetrical metal bis-acetylides trans-[(dppm)2M(C≡C-R)(C≡C-R′)]; (M = Ru, Os; R = C6H4-p-NO2, R′ = C6H5, C6H4-p-CH3; R = C6H5, R′ = C6H4-p-C6H3) using a variety of σ-acetylide coupling reactions is reported. Three compounds have been structurally characterised, including the unsymmetrical trans-[(dppm)2Os(C≡C-R)(C≡C-R′)] (R = C6H4-p-CH3, R′ = C6H4-p-NO2] which shows the 'rigid-rod' nature of the acetylide-metal-acetylide linkage. The electrochemistry of symmetrical and unsymmetrical Ru(II) complexes demonstrates the role of the acetylide and the auxiliary ligands in determining the ease of oxidation at the metal centre whilst UV-vis spectral changes illustrate the influence of electron-withdrawing and -donating ligands.

AB - The synthesis of a series of metal mono-acetylides trans-[(dppe)2Ru(Cl)(C≡C-R)] (R = C6H4-p-C6H5, C6H4-p-CH3, C6H4-p-NO2, C6H3-o-CH3-p-NO2, dppe = Ph2PCH2CH2PPh2), and unsymmetrical metal bis-acetylides trans-[(dppm)2M(C≡C-R)(C≡C-R′)]; (M = Ru, Os; R = C6H4-p-NO2, R′ = C6H5, C6H4-p-CH3; R = C6H5, R′ = C6H4-p-C6H3) using a variety of σ-acetylide coupling reactions is reported. Three compounds have been structurally characterised, including the unsymmetrical trans-[(dppm)2Os(C≡C-R)(C≡C-R′)] (R = C6H4-p-CH3, R′ = C6H4-p-NO2] which shows the 'rigid-rod' nature of the acetylide-metal-acetylide linkage. The electrochemistry of symmetrical and unsymmetrical Ru(II) complexes demonstrates the role of the acetylide and the auxiliary ligands in determining the ease of oxidation at the metal centre whilst UV-vis spectral changes illustrate the influence of electron-withdrawing and -donating ligands.

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