Further studies on the coordination chemistry of [Pt2(μ-S)2(PPh3)4] towards indium(III) substrates |
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| Authors: | William Henderson Allen G Oliver |
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| Institution: | a Department of Chemistry, University of Waikato, Private Bag 3105, Hamilton 3240, New Zealand
b Molecular Structure Facility, Department of Chemistry and Biochemistry, University of Notre Dame, Notre Dame, IN 46556, USA |
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| Abstract: | The reactivity of the metalloligand Pt2(μ-S)2(PPh3)4] towards a variety of indium(III) substrates has been explored. Reaction with excess In(NO3)3 and halide (KBr or NaI) gave the four-coordinate adducts Pt2(μ-S)2(PPh3)4InX2]+InX4]− (X = Br, I). An X-ray structure determination on the iodo complex revealed a slightly distorted tetrahedral coordination geometry at indium. In contrast, reaction of Pt2(μ-S)2(PPh3)4] with indium(III) chloride was more complex; the ion Pt2(μ-S)2(PPh3)4InCl2]+ was initially observed in solution (using ESI mass spectrometry), and isolated as its BPh4− salt. Analysis of Pt2(μ-S)2(PPh3)4InCl2]+BPh4]− by ESI MS showed the parent cation when analysed in MeCN solution. However in solutions containing methanol, partial solvolysis occurred to give the di-indium species {Pt2(μ-S)2(PPh3)4InCl(OMe)}2]2+ (proposed to contain an In2(μ-OMe)2 unit with five-coordinate indium) and its fragment ion Pt2(μ-S)2(PPh3)4InCl(OMe)]+. Reaction of Pt2(μ-S)2(PPh3)4] with InCl3·3H2O, 8-hydroxyquinoline (HQ) and trimethylamine in methanol gave the adduct Pt2(μ-S)2(PPh3)4InQ2]+, isolated as its PF6− salt. The same cationic complex is formed when Pt2(μ-S)2(PPh3)4] is reacted with InQ3 in methanol, but in this case the product is contaminated with the mononuclear complex (Ph3P)2PtQ]+ formed by disintegration of the trinuclear complex Pt2(μ-S)2(PPh3)4InQ2]+ with byproduct Q−. (Ph3P)2PtQ]+BPh4− was independently prepared from cis-PtCl2(PPh3)2] and HQ/Me3N, and is the first example of a platinum 8-hydroxyquinolinate complex containing phosphine ligands. |
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| Keywords: | Platinum complexes Indium complexes Sulfide ligands Crystal structure Electrospray ionisation mass spectrometry Ligand exchange reactions |
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