Synthesis and Structure of Pd4(-PtBu2)2(
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- 作者：Piero Leoni ; Marco Pasquali ; Luca Fadini ; Alberto Albinati ; Peter Hofmann ; and Markus Metz
- 刊名：Journal of the American Chemical Society
- 出版年：1997
- 出版时间：September 17, 1997
- 年：1997
- 卷：119
- 期：37
- 页码：8625 - 8629
- 全文大小：225K
- 年卷期：v.119,no.37(September 17, 1997)
- ISSN：1520-5126
文摘
The dinuclear CS2 complex[Pd2(
-PtBu2)(,
2:2-CS2)(PPh3)2]BF4,(2)BF4, reacts with Me4NI toyieldthe neutral tetranuclear Pd(I) derivativePd4(-PtBu2)2(4-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(-PtBu2)(-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(-PtBu2)(PPh3)3]BF4with Me4NI.
-PtBu2)(,2:2-CS2)(PPh3)2]BF4,(2)BF4, reacts with Me4NI toyieldthe neutral tetranuclear Pd(I) derivativePd4(-PtBu2)2(4-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(-PtBu2)(-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(-PtBu2)(PPh3)3]BF4with Me4NI.