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)2{μ3-{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)}2{μ3{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 language | English |
---|---|
Pages (from-to) | 1202-1210 |
Number of pages | 9 |
Journal | Helvetica Chimica Acta |
Volume | 82 |
Issue number | 8 |
DOIs | |
Publication status | Published - 01 Jan 1999 |
Externally published | Yes |
ASJC Scopus subject areas
- Catalysis
- Biochemistry
- Drug Discovery
- Physical and Theoretical Chemistry
- Organic Chemistry
- Inorganic Chemistry