Synthese und Eigenschaften des Differriosulfans {CpFe(CO)2}2S und der Di- und Triferriosulf (ox)onium-Salze [{CpFe(CO)2}2S(O)nCl]Cl (n=0, 1) und [{CpFe(CO)2}3S]Cl
作者:Ingo-Peter Lorenz、Kerstin Thurow
DOI:10.1016/0022-328x(95)05485-8
日期:1995.7
The diferriosulphane CpFe(CO)(2)}(2)(mu-S) (1) can easily be prepared by the reaction of CpFe(CO)(2)Cl with S(SiMe(3))(2). The nucleophilicity of the bridging sulphur atom in 1 is established by the addition of the electrophilic complex cation [CpFe(CO)(2)](+), giving the trinuclear complex [CpFe(CO)(2)}S-3]Cl (2), which can also be prepared by the reaction of S(SiMe(3))(2) with an excess of CpFe(CO)(2)Cl. Oxidation of 1 yields the SO2 complex 4, which easily eliminates one CO group by photolysis to form the CO-bridged complex 5. The triferriosulphonium salt 2 decarbonylates, too, and gives 6 containing one Fe-Fe bond and one CO bridge. The reaction of CpFe(CO)(2)}(2) with the sulphur chlorides SCl2 or SOCl2 leads to the formation of ionic S-functionalized species. The sulphur-containing fragments SCl or SOCl insert into the Fe-Fe bond to give the chloro-substituted diferriosulphonium or diferriosulphoxonium salts [CpFe(CO)(2)}2SCl]Cl (7) or [CpFe(CO)(2)}S-2(O)Cl]Cl (8). The mass, IR and NMR spectra of 1-8 are reported and discussed.