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Conventional and Cyclometallated Complexes of Ruthenium(II) with Ambidentate Terdentate Ligands Displaying N3 or N2C Binding Modes

DOI: 10.1039/DT9950000825

Source and publish data:

Journal of the Chemical Society, Dalton Transactions p. 825 - 834 (1995)

Update date:2022-08-03

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Authors:

Bardwell, David A.Bardwell, David A.

Jeffery, John C.Jeffery, John C.

Schatz, ErikSchatz, Erik

Tilley, Elizabeth E. M.Tilley, Elizabeth E. M.

Ward, Michael D.Ward, Michael D.

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Article abstract of DOI:10.1039/DT9950000825

The potentially terdentate N-donor ligands 6-(2-dimethylaminophenyl)-2,2'-bipyridine (L1) and 2-(2-dimethylaminophenyl)-1,10-phenanthroline (L2), which comprise a dimethylaminophenyl group attached to 2,2'-bipyridine or 1,10-phenanthroline fragments respectively, have been prepared.The ruthenium(II) complexes 2 (L = L1 1 or L2 2) and (L = L1 3 or L2 4) have been prepared and characterised by conventional spectroscopic, electrochemical and X-ray diffraction methods.In complexes 1 and 2 the ligands both co-ordinate in the expected N3-donor mode to give RuN6 centres.The Ru-N(amine) bonds (2.22 and 2.24 Angstroem respectively) are considerably longer than the Ru-N(pyridine) bonds (2.0-2.1 Angstroem).In complexes 3 and 4 one ligand is bound as a conventional N3 donor, but in the second the phenyl ring is turned around such that it co-ordinates in a cyclometallated fashion via C6 with the NMe2 substituent directed outwards.The Ru-C bonds (ca. 2.03 Angstroem) are similar in length to typical Ru-N(pyridine) bonds, and their strongly electron-donating capability results in a lengthening of the trans Ru-N bonds.Detailed comparison of the structures of 1 with 3, and 2 with 4, allows the structural effects of cyclometallation to be clarified.The Ru(II)-Ru(III) couples for 1 and 2 are cathodically shifted by ca. 0.1 V with respect to the RuN6 centre of (2+) (terpy = 2,2':6',2"-terpyridine) which is consistent with the greater ?-donating and poorer ?-accepting characteristics of tertiary amine ligands compared to pyridines: for 3 and 4, where the formally anionic carbon donor is a much stronger ? donor, the Ru(II)-Ru(III) couple is shifted cathodically by a further 0.84 V in each case.The electronic spectra of 1-4 are also discussed.

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Product name:2-(2-Dimethylaminophenyl)-1,10-phenanthroline

Cas No:162151-78-2

162151-78-2

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