Co-ordination chemistry of higher oxidation states. Part 2. Neutral and cationic complexes of platinum(IV) with bi- and multi-dentate ligands
- 1 January 1981
- journal article
- research article
- Published by Royal Society of Chemistry (RSC) in J. Chem. Soc., Dalton Trans.
- No. 11,p. 2153-2158
- https://doi.org/10.1039/dt9810002153
Abstract
Octahedral platinum(IV) complexes [Pt(L–L)X4][X = Cl or Br, L–L = Me2NCH2CH2NMe2, Ph2PCH2CH2PPh2, cis-Ph2PCHCHPPh2, Me2As(CH2)3AsMe2, o-C6H4(AsMe2)2, o-C6H4(AsPh2)2, cis-Ph2AsCHCHAsPh2, o-C6H4(SbPh2)2, Me2Sb(CH2)3SbMe2, or (SbMe3)2] have been prepared by oxidation of [Pt(L–L)X2] with halogen (X2) in CCl4. The amine, phosphine, and arsine complexes are very stable thermally and in solution, but the stabines decompose slowly at ambient temperature and immediately in solution. Decomposition of [Pt{Me2Sb(CH2)3SbMe2}Cl4] in solution gives [Pt{Me2Sb(CH2)3SbMe2}Cl2], Me2Sb(Cl2)(CH2)3Sb(Cl2)Me2, and other products. Several unstable [Pt(L–L)l4] complexes have been prepared, which lose iodine very easily and are partially dissociated in solution. Chlorine oxidation of [Pt(L′–L′)2Cl2][L′–L′=o-C6H4(AsMe2)2, Me2PCH2CH2PMe2, or o-C6H4(PMe2)(AsMe2)] produced trans-[Pt(L′–L′)2Cl2]Cl2, but for L′–L′=o-C6H4(AsPh2)2 or cis-Ph2AsCHCHAsPh2 the product was [Pt(L′–L′)Cl4] and oxidised ligand. The complex [Pt(Ph2PCH2CH2PPh2)2Cl2] gave [Pt(L–L)Cl4] on chlorine oxidation in solution, but Pt(L–L)2Cl4 when oxidised in a CCl4 suspension. The syntheses of mer-[Pt{PPh(CH2CH2PPh2)2}X3]X, mer-[Pt{AsMe(CH2CH2AsMe2)2}X3]X (X = Cl or Br),[Pt{P(CH2CH2PPh2)3}Cl2]Y2, [Pt{As(CH2CH2CH2AsMe2)3}Cl2]Cl2, [Pt{(CH2PPhCH2CH2PPh2)2}Cl2]Y2, and [Pt{o-C6H4[As(Me)CH2CH2CH2AsMe2]2}Cl2]Cl2(Y = Cl or ClO4) are described. Complexes were characterised by i.r., electronic, and 1H n.m.r. spectroscopy, and conductivity measurements.Keywords
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