Thiocarbonyl complexes of iron

Dunker, Jan
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Reaction of CpFe(CO)(,2)(CS)('+) with NaH gives cis- andtrans-CpFe(CO)(CS)(,2). The isomers can be separated bychromatography and fractional crystallization to give pure cis-;CpFe(CO)(CS)(,2) and pure trans-CpFe(CO)(CS)(,2). The transisomer has been shown to slowly isomerize in xylene at 50(DEGREES)C. AnX-ray crystal structure of cis-CpFe(CO)(CS)(,2) shows the CSligands to be in the bridging positions, but otherwise, its structureis nearly identical to that of cis-CpFe(CO)(,2)(,2). Reaction ofCpFe(CO)(CS)(,2) with the Lewis acid, HgCl(,2), gives;Cp(,2)Fe(,2)(CO)(,2)(CS)(CS-HgCl(,2)), where one of the bridging CSligands is coordinated to the Hg. The compound cis-Cp(,2)Fe(,2)(CO)(,2)(CS)(CSCH(,3))('+), containing a methylated bridgingthiocarbonyl ligand, is formed by reaction of cis-CpFe(CO)(CS)(,2)with CH(,3)OSO(,2)F or by reaction of cis- or trans-CpFe(CO)(CS)(,2)with CH(,3)I. Oxidation of CpFe(CO)(CS)(,2) by Br(,2) yieldsCpFe(CO)(CS)Br; this reaction apparently proceeds throughthe intermediate CpFe(CO)(CS)(,2)Br('+);Photolysis of CpFe(CO)(,2)(CS)X in (1) CH(,2)Cl(,2) yieldsCpFe(CO)(CS)CF(,3)SO(,3) (X = CF(,3)SO(,3)), (2) acetone yieldsCpFe(CO)(CS)(acetone)PF(,6) (X = PF(,6)), and (3) CH(,3)CNyields CpFe(CS)(CH(,3)CN)(,2)X (X = PF(,2), CF(,3)SO(,3)). Thecomplexes CpFe(CO)(CS)CF(,3)SO(,3) and CpFe(CS)(CH(,3)CN)(,2)X;are useful in the synthesis of other thiocarbonyl complexes.Reactions of CpFe(CO)(CS)CF(,3)SO(,3) with halide ions or GroupVA or VIA ligands yield complexes of the form CpFe(CO)(CS)X(X = Cl, Br, I) or CpFe(CO)(CS)(L)CF(,3)SO(,3) (L = PPh(,3), py,CH(,3)CN) and mixtures of CpFe(CO)(CS)(L)CF(,3)SO(,3) and;CpFe(CS)(L)(,2)CF(,3)SO(,3) (L = P(OMe)(,3), P(OPh)(,3), n-Bu(,2)S). Reactionof CpFe(CS)(CH(,3)CN)(,2)PF(,6) with Group VA ligands yieldsCpFe(CS)(L)(,2)PF(,6) when (L)(,2) = bipy, phen or L = PPh(,3) andCpFe(CS)(CH(,3)CN)(L)PF(,6) when L = P(OMe)(,3) or P(OPh)(,3).Three complexes--CpFe(CS)(PEt(,3))Cl, CpFe(CS)(PEt(,3))(,2)PF(,6)and CpFe(CS)(CH(,3)CN)(PEt(,3))PF(,6)--are formed when;CpFe(CS)(CH(,3)CN)(,2)PF(,6) reacts with PEt(,3). The novel dithiocarbonylcomplexes, CpFe(CS)(,2)X (X = I, Br) are formed by reaction ofCpFe(CS)(CH(,3)CN)(,2)PF(,6) with halide ions. Thermal reaction ofCpFe(CO)(CS)I with Group VA ligands yields CpFe(CO)(CS)(L)Iand CpFe(CS)(L)I when L = PEt(,3) and only CpFe(CS)(L)I whenL = PPh(,3), AsPh(,3), SbPh(,3), P(OMe)(,3), and P(OPh)(,3).(,)

Chemistry, Inorganic chemistry