Cyanide-bridged complexes with Sn(II)Mn(I), Sn(II)Mn(II), Sn(IV)Mn(I) and Sn(IV)Mn(II) oxidation states

  1. Anderson, K.M. 1
  2. Connelly, N.G. 1
  3. Goodwin, N.J. 1
  4. Lewis, G.R. 1
  5. Moreno, M.T. 1
  6. Orpen, A.G. 1
  7. Wood, A.J. 1
  1. 1 University of Bristol
    info

    University of Bristol

    Brístol, Reino Unido

    ROR https://ror.org/0524sp257

Revista:
Journal of the Chemical Society-Dalton Transactions

ISSN: 0300-9246

Año de publicación: 2001

Volumen: 9

Páginas: 1421-1427

Tipo: Artículo

DOI: 10.1039/B100721L SCOPUS: 2-s2.0-0034742886 GOOGLE SCHOLAR

Otras publicaciones en: Journal of the Chemical Society-Dalton Transactions

Repositorio institucional: lock_openAcceso abierto Editor

Resumen

The redox-active cyanomanganese carbonyl ligands trans- and cis-[Mn(CN)(CO)2(PR3)(dppm)] (R = OEt or OPh, dppm = Ph2PCH2PPh2) and trans-[Mn(CN)(CO)(dppm)2] react with SnCl2 to give [Cl2SnII(μ-NC)MnILx] [Lx = trans- and cis-(CO)2(PR3)(dppm), R = OEt or OPh, 1-4, and trans-(CO)(dppm)2 5]; complex 5 is oxidised by [Fe(η-C5H5)2][PF6] to give [Cl2SnII(μ-NC)MnII(CO)(dppm) 2][PF6] 5+[PF6]-. X-Ray structural studies on the redox related pair 5 and 5+ are consistent with oxidation localised mainly at Mn although the SnII-NC distance increases from 2.198(3) Å in 5 to 2.303(9) Å in 5+. The dicarbonyl cyanomanganese ligands react with SnCl4 to give trinuclear trans-[Cl4Sn{(μ-NC)MnLx}2] [Lx = trans- and cis-(CO)2(PR3)(dppm), R = OEt or OPh, 6-9], X-ray studies on 7 showing octahedral geometry at Sn(IV). The reaction of cis-[Mn(CN)(CO)2{P(OEt)3}(dppm)] with one equivalent each of SnCl4 and PPh3 and of trans-[Mn(CN)(CO)(dppm)2] with one equivalent each of SnCl4 and [N(PPh3)2]Cl gives heterobinuclear [Cl4 (Ph3P)SnIV(μ-NC)MnI(CO)2{P (OEt)3}(dppm)-cis] 10 and [N(PPh3)2][Cl5SnIV (μ-NC)-MnI(CO)(dppm)2-trans], [N(PPh3)2]+(11-), respectively; the latter is oxidised with [Fe(η-C5H5)2][PF6] to give [Cl5SnIV(μ-NC)MnII(CO)(dppm) 2-trans] 11, completing a series of cyanide-bridged complexes with core oxidation states Sn(II)Mn(I), Sn(II)Mn(II), Sn(IV)Mn(I) and Sn(IV)Mn(II).