Solid-State Structures and Solution Studies of Novel Cyclopentadienyl Mercury Compounds
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- 作者：Abdessamad Grirrane ; Irene Resa ; Diego del Rí ; o ; Amor Rodrí ; guez ; Eleuterio Á ; lvarez ; Kurt Mereiter ; Ernesto Carmona
- 刊名：Inorganic Chemistry
- 出版年：2007
- 出版时间：May 28, 2007
- 年：2007
- 卷：46
- 期：11
- 页码：4667 - 4676
- 全文大小：613K
- 年卷期：v.46,no.11(May 28, 2007)
- ISSN：1520-510X
文摘
New mercury cyclopentadienyl complexes Hg(
<SUP>1-Cp')Cl have been prepared by the reaction of HgCl2 and theappropriate KCp' salts or by the transmetalation of HgCl2 with ZnCp'2 (Cp' = C5Me4H, 1; C5Me4But, 2; C5Me4SiMe3, 3; C5H4SiMe3, 4). By contrast, only the SiMe3-substituted bis(cyclopentadienyl) derivatives, Hg(C5Me4SiMe3)2(5) and Hg(C5H4SiMe3)2 (6), can be isolated by the above synthetic procedures and the appropriate ratio of reagentsor from HgCp'Cl and KCp'. Solution NMR studies reveal nonfluxional behavior of the SiMe3-substituted complexes3, 5, and 6. X-ray studies of the solid-state structures show that the six compounds contain 1-Cp' ligands, withlinear or almost linear C-Hg-Cl or C-Hg-C coordination environments. The two HgCp'2 compounds, 5 and 6,have the expected insular structures, but the HgCp'Cl derivatives show supramolecular associations by means ofweak secondary Hg···Cl interactions. Thus, the HgCp'Cl compounds 1, 3, and 4 form three different polymericchain structures with typically two Hg···Cl interactions of 3.04-3.46 Å per mercury. By contrast, 2 forms a tetramer,[Hg(C5Me4SiMe3)Cl]4, with a cubelike arrangement of four Hg and four Cl atoms. Density functional theory hasbeen used to investigate the electronic structure of the compounds.
<SUP>1-Cp')Cl have been prepared by the reaction of HgCl2 and theappropriate KCp' salts or by the transmetalation of HgCl2 with ZnCp'2 (Cp' = C5Me4H, 1; C5Me4But, 2; C5Me4SiMe3, 3; C5H4SiMe3, 4). By contrast, only the SiMe3-substituted bis(cyclopentadienyl) derivatives, Hg(C5Me4SiMe3)2(5) and Hg(C5H4SiMe3)2 (6), can be isolated by the above synthetic procedures and the appropriate ratio of reagentsor from HgCp'Cl and KCp'. Solution NMR studies reveal nonfluxional behavior of the SiMe3-substituted complexes3, 5, and 6. X-ray studies of the solid-state structures show that the six compounds contain 1-Cp' ligands, withlinear or almost linear C-Hg-Cl or C-Hg-C coordination environments. The two HgCp'2 compounds, 5 and 6,have the expected insular structures, but the HgCp'Cl derivatives show supramolecular associations by means ofweak secondary Hg···Cl interactions. Thus, the HgCp'Cl compounds 1, 3, and 4 form three different polymericchain structures with typically two Hg···Cl interactions of 3.04-3.46 Å per mercury. By contrast, 2 forms a tetramer,[Hg(C5Me4SiMe3)Cl]4, with a cubelike arrangement of four Hg and four Cl atoms. Density functional theory hasbeen used to investigate the electronic structure of the compounds.