Molecular structures of 1,1'-bis(diphenylphosphino)ferrocene oxide and sulphide and their thermal properties

Article abstract of DOI:10.1016/0277-5387(95)00072-Z

The crystal and molecular structure of anhydrous 1,1'-bis(diphenylphosphino)ferrocene sulphide, Fe[C5H4P(S)Ph2]2 (dppfS2), is reported and compared with the hydrated oxide analogue, Fe[C5H4P(O)Ph2]2*2H2O (dppfO2*2H2O). It consits of two phosphoryl cyclopentadienyl rings [P-S =1.938(2) ?] sandwiching an Fe(II) centre. With four molecules per cell, the molecule is crystallographically required to sit on an inversion centre andhence the two rings are staggered. The thermal properties of [Fe(C5H4PP h2)2] (dppf), dppfO2*2H2O and dppfS2 were studied together with Fe(Cp)2 and Ph3PO*H2O by TGA and DSC. The thermal stability decreases in the order dppfO2>dppf>dppfS2. The hydrogen-bonded hydrate in dppfO2*2H2O is removed upon heating to 110-160°C.