Darstellung und Reaktionen von zweikernigen Platin(II)-Komplexen; Einkristall-Röntgenstrukturanalyse eines Tetrakis(difluorphosphonato)-Palladat(II)-Komplexes / Preparation and Reactions of Binuclear Platinum(II) Complexes. Single Crystal X-Ray Diffraction Study of a Tetrakis(difluorophosphonato)palladate(II) Complex

Abstract

o-Methylbenzyldifluorophosphite 2 was obtained by the reaction of o-methylbenzyltrimethyl silyl ether 1 with chlorodifluorophosphine PF2Cl. The reaction of 2 with the palladium(II) complex 3 led to the tetrakis(difluorophosphonato)palladate(II) complex 7. The X-ray structure analysis of 7 confirmed the nearly exact square planar structure at the metal atom of the tetrakis(difluorophosphonato)palladate(II) dianion. Minimal deviations from the ideal geometry at palladium and phosphorus are mainly the result of thermal motion or disorder phenomena in the crystal. In the reaction of the platinum(II) complex 8 with chlorodifluorophosphine the binuclear tetrakis(chlorodifluorophosphine)platinum(II)chloro complex 9 was obtained. In acetonitrile, 9 was cleaved to form the mononuclear complex 10. Similar results were obtained in the oxidative addition reactions of the platinum(0) complex 11 with sulfuryl chloride fluoride, 12, sulfuryl fluoride, 13, and phosphorus pentafluoride. Tetrakis-(triphenylphosphine)-μ-dichlorodiplatinum(II) hexafluorophosphate 14 was isolated. In acetonitrile the mononuclear acetonitrile-bis(triphenylphosphine)chloroplatinum(II) hexafluorophosphate complex 15 was isolated.