Preparation and characterization of rhodium(iii), iridium(iii) and ruthenium(ii) bearing 1,3- or 1,4-dithianesElectronic supplementary information (ESI) available: Crystal data and ORTEP figures for 2b, 2ab and 3c and further experimental details. See http://www.rsc.org/suppdata/dt/b3/b306496d/

Abstract

Reactions of [Cp*MCl2]2 (1a: M = Rh, 1b: M = Ir) or [(arene)RuCl2]2 (1c: arene = p-cymene; 1d: arene = C6Me6) with 1,3-dithiane (1,3-S2C4H8) gave [{LMCl2}2(1,3-S2C4H8)] 2 and [(LMCl2)( 1,3-S2C4H8)] 3 (LM = Cp*Rh, Cp*Ir, or (p-cymene)Ru, (C6Me6)Ru), depending on molar ratios between 1 and 1,3-dithiane. The reaction in the presence of KPF6 afforded the corresponding ionic complexes [LMCl(1,3-S2C4H8)2](PF6) 4. Complex 3a was treated with 1b, affording the heterobinuclear complex [Cp*RhCl2(1,3-S2C4H8)IrCl2Cp*] 2ab. Complex 2ab was obtained by a similar reaction of 3b with 1a, whereas reactions of 1c with 3a or 3b gave homonuclear complexes 2c and 2a (or 2b). Ionic complexes 4 were treated with 1, generating homo- or hetero-trinuclear complexes [{LMCl(1,3-S2C4H8)2}(L′MCl2)2](PF6) 5 (LM = Cp*Ir, L′M = Cp*Rh, Cp*Ir, or (p-cymene)Ru: LM = Cp*Rh, L′M = (p-cymene)Ru). Reactions of 1 with 1,4-dithiane (1,4-S2C4H8) were carried out in a 1 ∶ 1 molar ratio, generating binuclear complexes [(Cp*MCl2)2(1,4-S2C4H8)] (6a: M = Rh; 6b: M = Ir) or [{(arene)RuCl2}2(1,4-S2C4H8)] (arene = p-cymene (6c), C6Me6 (6d)). Reaction of 1a with an excess of 1,4-dithiane afforded a neutral mononuclear complex [Cp*RhCl2(1,4-S2C4H8)] 7a, whereas the reactions of 1b or 1c generated the corresponding ionic complexes [Cp*IrCl(1,4-S2C4H8)](Cl) 8b and [(p-cymene)RuCl(1,4-S2C4H8)](Cl) 8c. Treatment in the presence of KPF6 gave ionic complexes [LM(1,4-S2C4H8)](PF6) (LM = Cp*Rh (9a), Cp*Ir (9b), (p-cymene)Ru (9c)) Structures of 2a, 2ab, 3a, 3c, 4a, 8b and 9c were confirmed by X-ray analyses.