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Reactivity of the P-N Bond in the Halide Salts of Bisplatinum(II)

DOI: 10.1039/DT9950002005

Source and publish data:

Journal of the Chemical Society, Dalton Transactions p. 2005 - 2012 (1995)

Update date:2022-08-04

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Authors:

Browning, C. ScottBrowning, C. Scott

Farrar, David H.Farrar, David H.

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Article abstract of DOI:10.1039/DT9950002005

Conductivity measurements and 31P-<1H> NMR spectroscopy suggested that the chloride and iodide salts of bisplatinum(II) (2+) 1 exist in solution equilibrium with the five-co-ordinate complexes (1+) (X = Cl or I).The magnitude of the interaction of the iodide ion with 1 is greater than that of the chloride ion.The extent of formation of the halide-associated species is dependent upon the nature of the solvent.Association equilibrium constants Kassoc = 0.0718 and 0.315 mol dm-3 respectively were calculated for the chloride and iodide salts of 1 in MeNO2.Addition of trace quantities of water to solutions of the chloride or iodide salts of 1 effected cleavage of both P-N bonds of one of its dppma ligands giving >(1+) 2.The structure of the cation was investigated crystallographically as a mixture of the iodide and tetrafluoroborate salts of the form I0.210.79.The analogous reaction of the chloride salt of 1 with MeOH produces cleavage of only one P-N bond to give (2+) 3 as the chloride salt.Phosphorus-nitrogen bond solvolysis of both ligands of 1 occurs to give the complex trans- 4 upon addition of 2 equivalents of sodium cyanide to methanolic solvent mixtures of X2 (X = BF4, Cl or I).The product was characterised crystallographically.Possible mechanisms of formation of these complexes are discussed.

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