Oxidationsreaktionen von Phosphanen mit Schwefeldioxid/Oxidation Reactions of Phosphanes with Sulfur Dioxide

Sulfur dioxide can be used as an oxidizer in the reaction of Zn(SO 2 ) n (AsF 6 ) 2 and tetraphenyldiphosphane. The resulting product is the tetraphenyldiphosphane dioxide complex of composition Zn[O 2 P 2 (C 6 H 5 ) 4 ] 3 (AsF 6 ) 2 (1)-The same compound is formed by the direct reaction of the zinc salt with O 2 P 2 (C 6 H 5 ) 4 . When Zn(S0 2 )n(AsF 6 ) 2 is treated with P[O = P(OC 2 H 5 ) 2 ] 3 in liquid SO 2 , Zn{P[O = P(OC 2 H 5 ) 2 ] 3 } 2 (AsF 6 ) 2 (2) is formed. The structure of 2 was investigated by means of an X-ray single crystal analysis. 2 crystallizes in space group P3̄1 c with a = b= 11.967(3) and c = 21.202(4) Å. P[O = P(OC 2 H 5 ) 2 ] 3 and (CO) 4 W(CH 3 CN) 2 react to form (CO) 4 WP[O = P(OC 2 H 5 ) 2 ] 3 CH 3 CN.Only one acetonitrile molecule is replaced by the phosphane.