New aliphatic and aromatic thiolato-bridged complexes of palladium(II) and platinum(II)

Abstract

The hydroxo binuclear complexes [NBu 4] 2[}M(C 6F 5) 2(μ-OH){ 2] (M = Pd or Pt) react with thiols in methanol at room temperature to give the binuclear di-μ-thiolato complexes [NBu 4] 2[}M(C 6F 5) 2(μ-SR){ 2] (M = Pd, R = Et 1, t-Bu 2, C 6H 5, 3, and p-MeC 6H 4 4; M = Pt, R = Et 5, t-Bu 6, C 6H 5 7 or p-MeC 6H 4 8). The trinuclear palladium complexes [NBu 4] 2[(C 6F 5) 2Pd(μ-SEt) 2Pd(μ-SEt) 2Pd(C 6F 5) 2] 9 or [NBu 4] 2[(C 6 5) 2Pd(μ-1,2-S 2C 6H 4)Pd(μ-1,2-S 2C 6H 4)Pd(C 6F 5) 2] 10 have been obtained by reaction of the binuclear hydroxo palladium complex [NBu 4] 2[}Pd(C 6F 5) 2(μ-OH){ 2] with an excess of EtSH in refluxing methanol or with an excess of C 6H 4(SH) 2-1,2, in methanol at room temperature, respectively. The mixed hydroxo-axolate bridged complexes [}M(C 6F 5) 2{ 2(μ-OH)(μ-L)] 2− M = Pd, L = pyrazolate (pz); M = Pt, L = pyrazolate (pz) or 3,5-dimethylpyrazolate (dmpz)]react with thiols (1 : 1 molar ratio) in methanol to give the corresponding mixed thiolato-azolate bridged palladium or platinum complexes [}M(C 6F 5) 2{ 2(μ-SR)(μ-L)] 2− (M = Pd, L = dmpz, R = C 6H 5, 11, p-MeC 6H 4 12; M = Pt, L = pz, R = C 6H 5 13, p-MeC 6H 4, 14, Et 15, t-Bu 16; L = dmpz, R = C 6H 5 17, R = p-MeC 6H 4 18, Et 19]. The complexes have been characterized by partial elemental analyses, conductance measurements and spectroscopic (IR and 1H and 19F NMR) methods.