MOLECULAR-STRUCTURES OF 1,1'BIS-(DIPHENYLPHOSPHINO)FERROCENE OXIDE AND SULFIDE AND THEIR THERMAL-PROPERTIES

The crystal and molecular structure of anhydrous 1,1'-bis(di-phenylpho sphino)ferrocene sulphide, Fe[C5H4P(S)Ph(2)](2) (dppfS(2)), is reporte d and compared with the hydrated oxide analogue, Fe[C5H4P(O)Ph(2)](2) . 2H(2)O (dppfO(2) . 2H(2)O). It consists of two phosphoryl cyclopenta dienyl rings [P-S = 1.938(2) Angstrom] sandwiching all Fe-II centre. W ith four molecules per cell, the molecule is crystallographically requ ired to sit on an inversion centre and hence the two rings are stagger ed. The thermal properties of [Fe(C(5)H(4)PPh(2))(2)] (dppf), dppfO(2) . 2H(2)O and dppfS(2) were studied together with Fe(Cp)(2) and Ph(3)P O . H2O by TGA and DSC. The thermal stability decreases in the order d ppfO(2) > dppf > dppfS(2). The hydrogen-bonded hydrate in dppfO(2) . 2 H(2)O is removed upon heating to 110-160 degrees C.