Different Ways To Distort a Tetracapped Tetrahedron on Route to Forming an E4M4 Cubane: The Case of [E4(Pd(PPh2Me)2)4][Ph2EX2]2 (E = Sb, X = Cl; E = Bi, X = Br)
Different Ways To Distort a Tetracapped Tetrahedron on Route to Forming an E4M4 Cubane: The Case of [E4(Pd(PPh2Me)2)4][Ph2EX2]2 (E = Sb, X = Cl; E = Bi, X = Br)
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扭曲四帽四面体以形成 E4M4 古巴烷的不同方法：[E4(Pd(PPh2Me)2)4][Ph2EX2]2 的情况（E = Sb，X = Cl；E = Bi，X = Br）
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发表时间：
1999
期刊：
影响因子：
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通讯作者：
J. Saillard
中科院分区：
文献类型：
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作者：
J. L. Stark;B. Harms;I. Y. Guzman;K. Whitmire;R. Gautier;‖. A. J. Halet;J. Saillard
四羟（二苯基甲基膦）钯与二苯基氯化锑或二苯基溴化铋反应生成[E_4（PdL_2）_4][Ph_2EX_2]_2（L = PPh_2Me，1：E = Sb，X = Cl; 2：E = Bi，X = Br），并对[Sb_4（PdL_2）_4][Ph_2SbCl_2]_2·0.5THF和[Bi_4（PdL_2）_4][Ph_2BiBr_2]_2进行了光谱和单晶X射线衍射表征。这些化合物是基于电子计数形式主义的富电子。额外的团簇电子可以通过第15族元素表现出高价态的能力来合理化，特别是那些表现出更多金属特征的元素，如Sb和Bi。通过EHT和DFT计算研究了化合物和相关物种的电子结构。其他立方烷衍生结构的关系，并讨论了结构相关的M4 E4假设集群的稳定性。化合物1和2热分解得到Bi 2 Pd和SbPd。
Tetrakis(diphenylmethylphosphine)palladium reacts with diphenylantimony chloride or diphenylbismuth bromide to give [E4(PdL2)4][Ph2EX2]2 (L = PPh2Me, 1: E = Sb, X = Cl; 2: E = Bi, X = Br) which have been characterized spectroscopically and by single-crystal X-ray diffraction for [Sb4(PdL2)4][Ph2SbCl2]2·0.5THF and [Bi4(PdL2)4][Ph2BiBr2]2. These compounds are electron-rich based on electron counting formalisms. The additional cluster electrons can be rationalized by the ability of group 15 elements to show hypervalency, particularly those elements such as Sb and Bi which show more metal character. The electronic structure of the compounds and of related species has been examined by EHT and DFT calculations. Relationships to other cubane-derived structures are derived, and the stability of structurally related M4E4 hypothetical clusters is discussed. Compounds 1 and 2 decompose thermally to give Bi2Pd and SbPd.