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Coordination chemistry of calix-phosphanes: Cooperativity in the assembly of a tetragold calixarene complex

Lookup NU author(s): Emeritus Professor Anthony Harriman


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Assemblage of the tetragold complex [L.(AuCl)4] from p-tertbutyl- calix[4]-(OCH2PPh2)4 (L) and [AuCl(tetrahydrothiophene)] was investigated by NMR and UV/Visible spectroscopic titrations. Three steps could be resolved and are assigned, respectively, to addition of one, two and four AuCl units to the macrocyclic ligand. At each stage of metallation, symmetrical species persist on the NMR time scale since the bound AuCl fragments migrate between the different phosphorus centers via both intra- and intermolecular processes. The derived stability constants (logβ1 = 4.4 ± 0.2, logβ2 = 7.0 ± 0.7, and logβ4 = 14.5 ± 2.0) indicate both positive and negative cooperativity during build-up of the tetranuclear species. An X-ray diffraction study made with crystals obtained from an L:Au (1:2) mixture revealed the formation of an unusual binuclear complex whose solid state structure comprises a polymeric chain of [L.AuCl] units linked by pseudo- tetrahedral Au+ ions, each generic unit containing a pendant linear PAuCl fragment. This polymeric species, with its two distinct binding modes, provides a simple rationale by which to explain the role of cooperativity in the overall assembly process.

Publication metadata

Author(s): Dieleman CB, Matt D, Harriman A

Publication type: Article

Publication status: Published

Journal: European Journal of Inorganic Chemistry

Year: 2000

Issue: 5

Pages: 831-834

ISSN (print): 1434-1948

ISSN (electronic):

Publisher: Wiley - VCH Verlag GmbH & Co


DOI: 10.1002/(SICI)1099-0682(200005)2000:5<831::AID-EJIC831>3.0.CO;2-2


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