Gold(I) and palladium(II) complexes containing the functionalized ylides triarylphosphonium cyanomethylide or 2-cyanoethylide (R3P=CHR', R'= CN, CH2CN)

José Vicente*, María Teresa Chicote, María Cristina Lagunas

*Corresponding author for this work

Research output: Contribution to journalArticlepeer-review

23 Citations (Scopus)

Abstract

The coordination properties of ylides R3P=CHCN and R3P=CHCH2CN were studied. Ylide R3P=CHCN reacts with [AuCl(tht)] (molar ratio 1:1, tht=tetrahydrothiophene) to give [AuCl{CH(PPh3)CN}] (1). Dinuclear complexes [(AuL)2-{μ-C(PR3)CN}]ClO4 · nH2O (n = 1, L = PPh3, R = Ph (2a) or Tol (= 4-MeC6H4) (2b); n = 0, R = Tol, L = P(pmp)3 (2c; pmp = 4- MeOC6H4 or AsPh3 (2d)) are the products of reactions between phosphonium salts (R3PCH2CN)ClO4 (R = Ph or Tol) and [Au(acac)L] (molar ratio 1:3, L = PPh3 or P(pmp)3; acacH = acetylacetone). The reaction of [Au(acac)PPh3] with (Ph3PCH2CH2CN)ClO4 (Au/P 2-5) gives the mononuclear complex [Au{CH(PPh3)CH2CN}(PPh3)]ClO4 · 0.5 H2O (3). Complexes 2b or 2c react with [Au(acetone)L]ClO4 (molar ratio 1:1, L = PPh3 or P(pmp)3), prepared in situ from [AuCl(L)] and AgClO4 in acetone, to give the corresponding trinuclear derivatives [(AuL)23-{C(PTol3)CN}(AuL)}](ClO4)2 (L = PPh3 (4a) or P(pmp)3 (4b)]. We attempted unsuccessfully to prepare single crystals of 4a or 4b or of the triflate salt [{Au(PPh3)}23{C(PTol3)CN}(AuPPh3)}] (TfO)2 · H2O (4a'), obtained by reacting 4a with 2 equiv. of KCF 3SO3. In complexes 2 and 4, two new types of coordination of the ylides R3P = CHCN are present. Attempts to coordinate three AuL groups to the N-atom of (R3PCCN)- induced by aurophilicity (see A and B) were unsuccessful. The reaction between PdCl2 and R3P=CHCN (molar ratio 1:2) gives trans-[PdCl2{CH(PTol3)CN}2] (5).

Original languageEnglish
Pages (from-to)1202-1210
Number of pages9
JournalHelvetica Chimica Acta
Volume82
Issue number8
DOIs
Publication statusPublished - 01 Jan 1999
Externally publishedYes

ASJC Scopus subject areas

  • Catalysis
  • Biochemistry
  • Drug Discovery
  • Physical and Theoretical Chemistry
  • Organic Chemistry
  • Inorganic Chemistry

Fingerprint Dive into the research topics of 'Gold(I) and palladium(II) complexes containing the functionalized ylides triarylphosphonium cyanomethylide or 2-cyanoethylide (R<sub>3</sub>P=CHR', R'= CN, CH<sub>2</sub>CN)'. Together they form a unique fingerprint.

Cite this