Issue 1, 2001

Ruthenium terpyridine complexes with mono- and bi-dentate dithioleneligands

Abstract

The reaction of [Ru(CO)2Cl(terpy)]PF6 (terpy = 2,2′∶6′∶2′′-terpyridine) with Na2mnt (mnt = S2C2(CN)2) initially produced [Ru(CO)2(mnt-κS )(terpy-κ3NN N ′′)] 1a, which rearranged to [Ru(CO)2(mnt-κ2SS ′)(terpy-κ2NN ′)] 1b in solution. The molecular structures of 1a and 1b indicate that the rearrangement proceeds via a five-coordinated complex with monodentate mnt and bidentate terpy. The reaction of [Ru(CO)2Cl(terpy)]PF6 with 3,4-toluenedithiol (H2tdt) gave [Ru(CO)2(tdt-κ2SS ′)(terpy-κ2NN ′)] 2b but [Ru(CO)2(tdt-κS )(terpy-κ3NN N ′′)] 2a was not identified. Thus, ruthenium complexes with bidentate dithiolene and bidentate terpyridine seem to be more stable than those with monodentate dithiolene and tridentate terpyridine. Neither [Ru(CO)2(pdt-κS )(terpy-κ3NN N ′′)] 3a nor [Ru(CO)2(pdt-κ2S )(terpy-κ2NN ′)] 3b (pdt = PhC(S)C(S)Ph) was obtained in the reaction of [Ru(CO)2Cl(terpy)]PF6 with the Cs+ salt of pdt2− in CH3OH under N2. The same reaction conducted under aerobic conditions afforded [Ru(CO)(C(O)OCH3)(SC(Ph)C(Ph)SC(O)OMe)(terpy-κ3NN N ′′)] 3 resulting from double addition of CO2 and CH3OH to the terminal sulfur of pdt and a carbonyl carbon of 3a, respectively, followed by esterification of the resultant [Ru(CO)(C(O)OCH3)(SC(Ph)C(Ph)SC(O)OH)(terpy-κ3NN N′′)] in CH3OH. The addition of CO2 to the sulfur of 3a is ascribed to the strong basicity and weak chelating ability of pdt compared with those of mnt and tdt. A series of [RuX(dithiolene)(terpy)]n+ (X = dmso, Cl or OSO2CF3; n = 0 or 1) were also prepared.

Supplementary files

Article information

Article type
Paper
Submitted
18 Sep 2000
Accepted
30 Oct 2000
First published
06 Dec 2000

J. Chem. Soc., Dalton Trans., 2001, 57-63

Ruthenium terpyridine complexes with mono- and bi-dentate dithiolene ligands

H. Sugimoto, K. Tsuge and K. Tanaka, J. Chem. Soc., Dalton Trans., 2001, 57 DOI: 10.1039/B007541H

To request permission to reproduce material from this article, please go to the Copyright Clearance Center request page.

If you are an author contributing to an RSC publication, you do not need to request permission provided correct acknowledgement is given.

If you are the author of this article, you do not need to request permission to reproduce figures and diagrams provided correct acknowledgement is given. If you want to reproduce the whole article in a third-party publication (excluding your thesis/dissertation for which permission is not required) please go to the Copyright Clearance Center request page.

Read more about how to correctly acknowledge RSC content.

Spotlight

Advertisements