Synthesis and structural characterization of binuclear half-sandwich iridium, rhodium and ruthenium complexes containing 4,4′-dipyridyldisulfide (4DPDS) ligandsElectronic supplementary information (ESI) available. CCDC reference numbers 767811(2a·Et2O), No. 767812(2c·2CH2Cl2), No. 767813 (3c·2CH2Cl2), and No. 767814 (3c·4CHCl3). For ESI and crystallographic data in CIF or other electronic format see DOI: 10.1039/c0dt00057d

Reactions of half-sandwich iridium and rhodium complexes [Cp*MCl2]2(1a: M = Ir, 1b: M = Rh) and the half-sandwich ruthenium complex [(p-cymene)RuCl2]2(1c) with 4DPDS gave the corresponding binuclear complexes [{Cp*MCl2]2}(μ-4DPDS) (2a: M = Ir, 2b: M = Rh) and [{(p-cymene)RuCl2]2}(μ-4DPDS) (2c), which can be converted into binuclear metallamacrocycles. The metallamacrocycles [Cp*M(μ-4DPDS)Cl]22+(3a: M = Ir, 3b: M = Rh) and [(p-cymene)Ru(μ-4DPDS)Cl]22+(3c) are composed of two half-sandwich units and two 4DPDS ligands with the same chirality. The macrocycle 3cis chiral and changes its shape slightly depending on the guests accommodated above and below the cavities. [ABSTRACT FROM AUTHOR]