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Issue 40, 2012
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Self-assembly of isomeric clamshell dimers of platinum(II)

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The controlled synthesis of isomeric organoplatinum clamshell dimers [Pt2Me223-6-dppd)2]2+, 6-dppd = 1,4-di-2-pyridyl-5,6,7,8,9,10-hexahydrocycloocta[d]pyridazine, is reported. The new complexes are formed selectively by self-assembly from mononuclear precursors, taking advantage of the slow cistrans isomerization at platinum(II). Thus reaction of endo-[PtClMe(κ2-6-dppd)] with AgOTf gave endo,endo-[Pt2Me223-6-dppd)2]2+, while the reaction of [PtMe22-6-dppd)] with HOTf in solvent S = Me2C[double bond, length as m-dash]O or MeCN gave first a mixture of exo- and endo-[PtMe(S)(κ2-6-dppd)]+ and then, by loss of solvent, a mixture of exo,exo- and endo,endo-[Pt2Me223-6-dppd)2]2+. The endo,endo isomer slowly isomerized to the more stable exo,exo isomer in solution. Reaction of PPh3 with endo-[PtClMe(κ2-6-dppd)] gave a mixture of endo- and exo-[PtMe(PPh3)(κ2-6-dppd)]+ but reaction with exo,exo-[Pt2Me223-6-dppd)2]2+ gave exo-[PtMe(PPh3)(κ2-6-dppd)]+ selectively, with retention of stereochemistry. The structures of the clamshell dimers and of key precursors are reported and equilibria are studied both experimentally and by DFT calculations.

Graphical abstract: Self-assembly of isomeric clamshell dimers of platinum(ii)

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Publication details

The article was received on 17 Jul 2012, accepted on 15 Aug 2012 and first published on 15 Aug 2012

Article type: Paper
DOI: 10.1039/C2DT31584J
Citation: Dalton Trans., 2012,41, 12378-12385

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    Self-assembly of isomeric clamshell dimers of platinum(II)

    M. S. McCready and R. J. Puddephatt, Dalton Trans., 2012, 41, 12378
    DOI: 10.1039/C2DT31584J

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