Full Paper

Spontaneous Formation of Heteroligated PtII Complexes with Chelating Hemilabile Ligands

  1. Pirmin A. Ulmann1,
  2. Aaron M. Brown1,
  3. Maxim V. Ovchinnikov1,
  4. Chad A. Mirkin Prof.1,
  5. Antonio G. DiPasquale2,
  6. Arnold L. Rheingold Prof.2

Article first published online: 29 MAR 2007

DOI: 10.1002/chem.200601837

Issue

Chemistry - A European Journal

Chemistry - A European Journal

Volume 13, Issue 16, pages 4529–4534, May 25, 2007

Additional Information

How to Cite

Ulmann, P., Brown, A., Ovchinnikov, M., Mirkin, C., DiPasquale, A. and Rheingold, A. (2007), Spontaneous Formation of Heteroligated PtII Complexes with Chelating Hemilabile Ligands. Chemistry - A European Journal, 13: 4529–4534. doi: 10.1002/chem.200601837

Author Information

  1. 1

    Department of Chemistry and the International Institute for Nanotechnology, Northwestern University, 2145 Sheridan Road, Evanston, Illinois 60208-3113, USA, Fax: (+1) 847-467-5123

  2. 2

    Department of Chemistry and Biochemistry, University of California, San Diego, 9500 Gilman Drive, La Jolla, California 92093-0358, USA

Publication History

  1. Issue published online: 15 MAY 2007
  2. Article first published online: 29 MAR 2007
  3. Manuscript Received: 20 DEC 2006

Funded by

  • NSF
  • ARO
  • AFOSR
  • DDRE (MURI)

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Keywords:

  • coordination modes;
  • hemilabile ligands;
  • platinum;
  • supramolecular chemistry;
  • transition metals

Graphical Abstract

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Metallosupramolecular chemistry: a novel ligand rearrangement process leads to the formation of the heteroligated complex [PtCl(κ2-Ph2PCH2CH2SMe)(Ph2PCH2CH2SPh)]Cl (shown here). Using the weak-link approach, closed and semi-open derivatives with varying relative arrangement of the alkyl and aryl groups can be synthesized. Analogous procedures using Ph2PCH2CH2SMe and 1,4-(Ph2PCH2CH2S)2C6H4 lead to bimetallic complexes, illustrating the assembly of complementary metallosupramolecular structures.

Abstract

The spontaneous formation of the heteroligated complex [PtCl(κ2-Ph2PCH2CH2SMe)(Ph2PCH2CH2SPh)]Cl (8 a) by a novel ligand rearrangement process has been observed. By using the weak-link approach, the relative arrangement of the alkyl and aryl groups can be controlled by abstraction of chloride from 8 a to form the closed complex [Pt(κ2-Ph2PCH2CH2SMe)(κ2-Ph2PCH2CH2SPh)][BF4]2 (5) and reopening using halide ions to form semi-open complexes [PtX(κ2-Ph2PCH2CH2SMe)(Ph2PCH2CH2SPh)]BF4 (8 b; X=Cl−) and (8 c; X=I−). Analogous procedures using Ph2PCH2CH2SMe and 1,4-(Ph2PCH2CH2S)2C6H4 lead to heteroligated bimetallic complexes 7 and 9, illustrating that this ligand rearrangement process can be used as a tool for the assembly of complementary metallosupramolecular structures.

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