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Coordination chemistry of the [Pt2(μ-S)2(PPh3)4] metalloligand with π-hydrocarbon derivatives of d ruthenium(II), osmium(II), rhodium(III) and iridium(III)
Authors:S-W Audi Fong  William Henderson  Brian K Nicholson  Sarah M Devoy
Institution:a Department of Chemistry, National University of Singapore, 3 Science Drive 3, Singapore 117543, Singapore
b Department of Chemistry, University of Waikato, Private Bag 3105, Hamilton, New Zealand
Abstract:The reactivity of Pt2(μ-S)2(PPh3)4] towards RuCl26-arene)]2 (arene=C6H6, C6Me6, p-MeC6H4Pri=p-cymene), OsCl26-p-cymene)]2 and MCl25-C5Me5)]2 (M=Rh, Ir) have been probed using electrospray ionisation mass spectrometry. In all cases, dicationic products of the type Pt2(μ-S)2(PPh3)4ML]2+ (L=π-hydrocarbon ligand) are observed, and a number of complexes have been prepared on the synthetic scale, isolated as their BPh4 or PF6 salts, and fully characterised. A single-crystal X-ray structure determination on the Ru p-cymene derivative confirms the presence of a pseudo-five-coordinate Ru centre. This resists addition of small donor ligands such as CO and pyridine. The reaction of Pt2(μ-S)2(PPh3)4] with RuClCp(PPh3)2 (Cp=η5-C5H5) gives Pt2(μ-S)2(PPh3)4RuCp]+. In addition, the reaction of Pt2(μ-S)2(PPh3)4] with the related carbonyl complex RuCl2(CO)3]2, monitored by electrospray mass spectrometry, gives Pt2(μ-S)2(PPh3)4Ru(CO)3Cl]+.
Keywords:Mixed-metal complexes  Sulfide ligands  Electrospray mass spectrometry  Platinum complexes  Organometallic complexes
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