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-κ 2NN′)] 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-κ 2NN′)] 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-κ2 NN′)] 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-κ3 NN′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-κ3 NN′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.
| Original language | English |
|---|---|
| Pages (from-to) | 57-63 |
| Number of pages | 7 |
| Journal | Journal of the Chemical Society - Dalton Transactions |
| Issue number | 1 |
| DOIs | |
| State | Published - 2001 |
ASJC Scopus subject areas
- General Chemistry