Octahedral Alkynylphosphine Ruthenium(II) Complexes: Synthesis, Structure, and Electrochemistry

  1. Berenguer, J. 1
  2. Bernechea, M. 1
  3. Fernández, J. 1
  4. Gil, B. 1
  5. Lalinde, E. 1
  6. Moreno, M.T. 1
  7. Ruiz, S. 1
  8. Sánchez, S. 1
  1. 1 Universidad de La Rioja
    info

    Universidad de La Rioja

    Logroño, España

    ROR https://ror.org/0553yr311

Journal:
Organometallics

ISSN: 0276-7333

Year of publication: 2011

Volume: 30

Issue: 17

Pages: 4665-4677

Type: Article

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DOI: 10.1021/OM2005194 SCOPUS: 2-s2.0-80052460866 WoS: WOS:000294647500028 GOOGLE SCHOLAR

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Abstract

Reaction of [RuCl2(PPh3)3] with excess of PPh2C≡CFc (Fc = ferrocenyl) proceeds with formation of [trans-RuCl2(PPh2C≡CFc)4] (3), which reacts with HC≡CR (R = Ph, Tol) via dissociative loss of one PPh 2C≡CFc ligand to yield vinylidene complexes [mer,cis-RuCl 2(C=CHR)(PPh2C≡CFc)3] (R = Ph 4a, Tol 4b). Reported herein also is the preparation of a series of trans/cis bis(alkynyl)tetrakis(alkynylphosphine) derivatives [Ru(C≡CR′) 2(PPh2C≡CR)4] (R′ = Ph, Tol; R = Ph, trans/cis-5a, 5b; R = Tol, trans/cis-6a, 6b; R = Fc, trans/cis-7a, 7b), synthesized by reaction of [trans-RuCl2(PPh2C≡CR) 4] (R = Ph 1, Tol 2, Fc 3) with an excess of HC≡CR′ (R′ = Ph, Tol) and NEt3, in the presence or absence of NaPF6. In the preparation of cis-5a, the ketovinyl derivative [mer-Ru{κC,O-C(CH2COCH3)=CHPh}Cl(PPh 2C≡CPh)3] (8) was obtained as a byproduct in the presence of acetone. The solid-state structures of complexes 3, trans-5a, trans-7a, and 8 have been determined by X-ray diffraction studies, showing the presence of several types of weak intramolecular hydrogen interactions. The cyclic voltammetry data for the mononuclear complexes (1, 2, trans/cis-5/6, and 8) show a quasi reversible oxidation attributed to the RuII/III couple and reveal a marked influence of the ligands and the geometry on the E1/2 values. The electrochemical behavior of the ferrocenylethynyldiphenylphosphine compounds 3, 4, and trans/cis-7 is more complex. Spectroelectrochemical comparative studies of related complexes (trans-7b vs trans-5b; 4 vs [RuCl2(C=CHTol)(PPh2C≡ CPh)3]) suggest that the first oxidation occurs at the ferrocene site of the PPh2C≡CFc ligand. © 2011 American Chemical Society.