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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-NO2)], [(dppe)2Ru(Cl)(CC–C6H3-o-CH3-p-NO2)] and [(dppm)2Os(CC–C6H4-p-CH3)(CC–C6H4-p-NO2)]

1999; Elsevier BV; Volume: 578; Issue: 1-2 Linguagem: Inglês

10.1016/s0022-328x(98)01123-1

1872-8561

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

Organometallic Complex Synthesis and Catalysis

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-CH3) 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.