Pt-Mg, Pt-Ca, and Pt-Zn Lantern Complexes and Metal-Only Donor-Acceptor Interactions

  1. Baddour, F.G. 2
  2. Hyre, A.S. 2
  3. Guillet, J.L. 2
  4. Pascual, D. 1
  5. Lopez-De-Luzuriaga, J.M. 1
  6. Alam, T.M. 3
  7. Bacon, J.W. 2
  8. Doerrer, L.H. 2
  1. 1 Universidad de La Rioja
    info

    Universidad de La Rioja

    Logroño, España

    ROR https://ror.org/0553yr311

  2. 2 Boston University
    info

    Boston University

    Boston, Estados Unidos

    ROR https://ror.org/05qwgg493

  3. 3 Sandia National Laboratories
    info

    Sandia National Laboratories

    Albuquerque, Estados Unidos

    ROR https://ror.org/01apwpt12

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Revue:
Inorganic Chemistry

ISSN: 0020-1669

Année de publication: 2017

Volumen: 56

Número: 1

Pages: 452-469

Type: Article

DOI: 10.1021/ACS.INORGCHEM.6B02372 SCOPUS: 2-s2.0-85008870866 WoS: WOS:000391248900051 GOOGLE SCHOLAR

D'autres publications dans: Inorganic Chemistry

Résumé

Pt-based heterobimetallic lantern complexes of the form [PtM(SOCR)4(L)] have been shown previously to form intermolecular metallophilic interactions and engage in antiferromagnetic coupling between lanterns having M atoms with open shell configurations. In order to understand better the influence of the carboxylate bridge and terminal ligand on the electronic structure, as well as the metal-metal interactions within each lantern unit, a series of diamagnetic lantern complexes, [PtMg(SAc)4(OH2)] (1), [PtMg(tba)4(OH2)] (2), [PtCa(tba)4(OH2)] (3), [PtZn(tba)4(OH2)] (4), and a mononuclear control (Ph4P)2[Pt(SAc)4] (5) have been synthesized. Crystallographic data show close Pt-M contacts enforced by the lantern structure in each dinuclear case. 195Pt-NMR spectroscopy of 1-4, (Ph4P)2[Pt(SAc)4] (5), and several previously reported lanterns revealed a strong chemical shift dependence on the identity of the second metal (M), mild influence by the thiocarboxylate ligand (SOCR; R = CH3 (thioacetate, SAc), C6H5 (thiobenzoate, tba)), and modest influence from the terminal ligand (L). Fluorescence spectroscopy has provided evidence for a Pt···Zn metallophilic interaction in [PtZn(SAc)4(OH2)], and computational studies demonstrate significant dative character. In all of 1-4, the short Pt-M distances suggest that metal-only Lewis donor (Pt)-Lewis acceptor (M) interactions could be present. DFT and NBO calculations, however, show that only the Zn examples have appreciable covalent character, whereas the Mg and Ca complexes are much more ionic. © 2016 American Chemical Society.