Study of the Coordination Abilities of Stibine Ligands to Gold(I).

  1. Bojan, V.R. 1
  2. Fernández, E.J. 1
  3. Laguna, A. 2
  4. López-De-Luzuriaga, J.M. 1
  5. Monge, M. 1
  6. Olmos, M.E. 1
  7. Puelles, R.C. 1
  8. Silvestru, C. 3
  1. 1 Universidad de La Rioja
    info

    Universidad de La Rioja

    Logroño, España

    ROR https://ror.org/0553yr311

  2. 2 Instituto de Nanociencia y Materiales de Aragón
    info

    Instituto de Nanociencia y Materiales de Aragón

    Zaragoza, España

    ROR https://ror.org/031n2c920

  3. 3 Babeș-Bolyai University
    info

    Babeș-Bolyai University

    Cluj, Rumanía

    ROR https://ror.org/02rmd1t30

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Revista:
Inorganic Chemistry

ISSN: 0020-1669

Año de publicación: 2010

Volumen: 49

Número: 12

Páginas: 5530-5541

Tipo: Artículo

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DOI: 10.1021/IC1003484 PMID: 20540566 SCOPUS: 2-s2.0-77953597410 WoS: WOS:000278615700030 GOOGLE SCHOLAR

Otras publicaciones en: Inorganic Chemistry

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Resumen

The reaction of [AuCl(tht)] (tht = tetrahydrothiophene) with SbMes nPh3-n (n = 3 (1), 2 (2), 1 (3)) produces the 1:1 adducts [AuCl(SbMesnPh3-n)] (n = 3 (4), 2 (5), 1 (6)), with a Sb-Au-Cl environment, regardless of the molar ratio used (1:1 to 1:4). Addition of the same stibines to [Au(tht)2]ClO4 (molar ratio 1:1 to 1:4) results in isolation of the 1:2 adducts [Au(SbMesnPh 3-n)2]ClO4 (n = 3 (7), 2 (10)), containing linear Sb-Au-Sb fragments, or the 1:3 adduct [Au(SbMesPh2) 3]ClO4 (11), with a quasi trigonal planar AuSb3 core. The same 1:2 cations are produced when [Au(tht)2]CF 3SO3 is reacted with 1 or following a rearrangement process when 4 is treated with AgSbF6, that is, [Au(SbMes 3)2]X (X = CF3SO3 (8), SbF 6 (9)). The compounds were characterized by spectroscopic methods, and the molecular structures of 2-4, 7, 8•2CDCl3, 9, and 11 were established by single-crystal X-ray diffraction. Theoretical calculations were carried out on model systems of type ER3 and [Au(ER3) n]+ (E = P or Sb; R = Ph or Mes; n = 2, 3, or 4) to gain insight into the bonding nature of SbR3 ligands in homoleptic gold-stibine adducts, in comparison with phosphine-gold(I) compounds. Steric effects govern the coordination of stibines with mesityl substituents. A preference for higher coordination numbers is observed for SbPh3 when compared with PPh3 and experimentally observed C-Sb-C and Sb-C structural distortions of stibines upon coordination are reproduced theoretically. © 2010 American Chemical Society.