title: Solid-state structures and solution studies of novel cyclopentadienyl mercury compounds.
abstract: New mercury cyclopentadienyl complexes Hg(eta1-Cp')Cl have been prepared by the reaction of HgCl2 and the appropriate 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 reagents or from HgCp'Cl and KCp'. Solution NMR studies reveal nonfluxional behavior of the SiMe3-substituted complexes 3, 5, and 6. X-ray studies of the solid-state structures show that the six compounds contain eta1-Cp' ligands, with linear 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 of weak secondary Hg...Cl interactions. Thus, the HgCp'Cl compounds 1, 3, and 4 form three different polymeric chain structures with typically two Hg...Cl interactions of 3.04-3.46 A 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 has been used to investigate the electronic structure of the compounds.
authors.affiliation: Instituto de Investigaciones Químicas, Departamento de Química Inorgánica, Consejo Superior de Investigaciones Científicas, Universidad de Sevilla, Avda. Américo Vespucio s/n, 41092 Sevilla, Spain.
authors.forename: Abdessamad
authors.initials: A
authors.lastname: Grirrane
authors.forename: Irene
authors.initials: I
authors.lastname: Resa
authors.forename: Diego
authors.initials: D
authors.lastname: del Río
authors.forename: Amor
authors.initials: A
authors.lastname: Rodríguez
authors.forename: Eleuterio
authors.initials: E
authors.lastname: Alvarez
authors.forename: Kurt
authors.initials: K
authors.lastname: Mereiter
authors.forename: Ernesto
authors.initials: E
authors.lastname: Carmona