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

doi:10.1016/S0022-328X(98)01123-1

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

^*Corresponding author for this work

Chemistry

Research output: Contribution to journal › Article › peer-review

58 Citations (Scopus)

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 language	English
Pages (from-to)	198-209
Number of pages	12
Journal	Journal of Organometallic Chemistry
Volume	578
Issue number	1-2
DOIs	https://doi.org/10.1016/S0022-328X(98)01123-1
Publication status	Published - Apr 22 1999

Keywords

Acetylide
Electrochemistry
Osmium
Ruthenium

ASJC Scopus subject areas

Biochemistry
Physical and Theoretical Chemistry
Organic Chemistry
Inorganic Chemistry
Materials Chemistry

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10.1016/S0022-328X(98)01123-1

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Younus, M., Long, N. J., Raithby, P. R., Lewis, J., Page, N. A., White, A. J. P., Williams, D. J., Colbert, M. C. B., Hodge, A. J., Khan, M. S., & Parker, D. G. (1999). 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)]. Journal of Organometallic Chemistry, 578(1-2), 198-209. https://doi.org/10.1016/S0022-328X(98)01123-1

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

Research output: Contribution to journal › Article › peer-review

Younus, M, Long, NJ, Raithby, PR, Lewis, J, Page, NA, White, AJP, Williams, DJ, Colbert, MCB, Hodge, AJ, Khan, MS & Parker, DG 1999, '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)]', Journal of Organometallic Chemistry, vol. 578, no. 1-2, pp. 198-209. https://doi.org/10.1016/S0022-328X(98)01123-1

Younus M, Long NJ, Raithby PR, Lewis J, Page NA, White AJP et al. 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)]. Journal of Organometallic Chemistry. 1999 Apr 22;578(1-2):198-209. doi: 10.1016/S0022-328X(98)01123-1

Younus, Muhammad ; Long, Nicholas J. ; Raithby, Paul R. et al. / 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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title = "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)]",

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.",

keywords = "Acetylide, Electrochemistry, Osmium, Ruthenium",

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

note = "Funding Information: The authors thank the Cambridge Commonwealth Trust for a Scholarship and Shahjalal University of Science and Technology, Bangladesh, for study leave (MY), the British Council (MCBC), ICI, Wilton (AH and NP) for financial assistance and Johnson Matthey PLC ({\textquoteleft}JM{\textquoteright}) for the loan of precious metals.",

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doi = "10.1016/S0022-328X(98)01123-1",

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T1 - Synthesis and characterisation of mono-acetylide and unsymmetrical bis-acetylide complexes of ruthenium and osmium

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.

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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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