| Abstract
| - The dinuclear CS2 complex[Pd2(μ-PtBu2)(μ,η2:η2-CS2)(PPh3)2]BF4,(2)BF4, reacts with Me4NI toyieldthe neutral tetranuclear Pd(I) derivativePd4(μ-PtBu2)2(μ4-CS2)(PPh3)2I2(4), which has been characterized by single-crystal X-ray diffraction. Its unusual molecular structure with aformally hexacoordinate carbon atom, as well asthat of (2)+ with a planar tetracoordinatecarbon can be explained on the basis of fragment MO considerationsandEHMO model calculations. The reaction proceeds stepwise, with therelatively fast substitution of CS2 by theiodideion giving the intermediate complexPd2(μ-PtBu2)(μ-I)(PPh3)2(3). The latter further reacts slowly with freeCS2 togive complex 4 and free PPh3. Complex3 was also prepared and isolated pure by reacting[Pd2(μ-PtBu2)(PPh3)3]BF4with Me4NI.
|
