Synthesis and Structure of Pd4(μ-PtBu2)2(μ-CS2)(PPh3)2I2, a Neutral Palladium(I) Derivative with a Hexacoordinate Carbon and a CS2 Molecule Bridging Four Palladium Centers
Synthesis and Structure of Pd4(μ-PtBu2)2(μ-CS2)(PPh3)2I2, a Neutral Palladium(I) Derivative with a Hexacoordinate Carbon and a CS2 Molecule Bridging Four Palladium Centers
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DOI：
10.1021/ja970262
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发表时间：
1997-09
影响因子：
15
通讯作者：
P. Leoni;M. Pasquali;L. Fadini;A. Albinati;P. Hofmann;M. Metz
中科院分区：
文献类型：
--
作者：
P. Leoni;M. Pasquali;L. Fadini;A. Albinati;P. Hofmann;M. Metz
The dinuclear CS2 complex [Pd2(μ-PtBu2)(μ,η2:η2-CS2)(PPh3)2]BF4, (2)BF4, reacts with Me4NI to yield the neutral tetranuclear Pd(I) derivative Pd4(μ-PtBu2)2(μ4-CS2)(PPh3)2I2 (4), which has been characterized by single-crystal X-ray diffraction. Its unusual molecular structure with a formally hexacoordinate carbon atom, as well as that of (2)+ with a planar tetracoordinate carbon can be explained on the basis of fragment MO considerations and EHMO model calculations. The reaction proceeds stepwise, with the relatively fast substitution of CS2 by the iodide ion giving the intermediate complex Pd2(μ-PtBu2)(μ-I)(PPh3)2 (3). The latter further reacts slowly with free CS2 to give complex 4 and free PPh3. Complex 3 was also prepared and isolated pure by reacting [Pd2(μ-PtBu2)(PPh3)3]BF4 with Me4NI.
