Synthesis and Characterization of the Homologous M-M Bonded Series Ar'MMAr' (M = Zn, Cd, or Hg; Ar' = C6H3-2,6-(C6H3-2,6-Pri2)2) and Related Arylmetal Halides and Hydride Species.

Zhongliang Zhu, Marcin Brynda, Robert J. Wright, Roland C. Fischer, W. Alexander Merrill, Eric Rivard, Robert Wolf, James C. Fettinger, Marilyn M. Olmstead, Philip P. Power

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The synthesis and structural characterization of the first homologous, mol. M-M bonded series for the group 12 metals are reported. The compds. Ar'MMAr' (M = Zn, Cd, or Hg; Ar' = C6H3-2,6-(C6H3-2,6-Pri2)2) were synthesized by redn. of the corresponding arylmetal halides by alkali metal/graphite (Zn or Hg) or sodium hydride (Cd). These compds. possess almost linear C-M-M-C core structures with two-coordinate metals. The obsd. M-M bonds distances were 2.3591(9), 2.6257(5), and 2.5738(3) Å for the zinc, cadmium, and mercury species, resp. The shorter Hg-Hg bond in comparison to that of Cd-Cd is consistent with DFT calcns. which show that the strength of the Hg-Hg bond is greater. The arylmetal halides precursors (Ar'MI)1 or 2, and the highly reactive hydrides (Ar'MH)1or2, were also synthesized and fully characterized by x-ray crystallog. (Zn and Cd) and multinuclear NMR spectroscopy. The arylzinc and arylcadmium iodides have iodide-bridged dimeric structures, whereas the arylmercury iodide, Ar'HgI, is monomeric. The arylzinc and arylcadmium hydrides have sym. (Zn) or unsym. (Cd) μ-H-bridged structures. The Ar'HgH species was synthesized and characterized by spectroscopy, but a satisfactory refinement of the structure was precluded by the contamination of monomeric Ar'HgH by Ar'H. It was also shown that the decompn. of Ar'Cd(μ-H)2CdAr' at room temp. leads to the M-M bonded Ar'CdCdAr', thereby supporting the view that the redn. of the iodide proceeds via the hydride intermediate. [on SciFinder(R)]
Original languageEnglish
Pages (from-to)10847-10857
Number of pages11
JournalJournal of the American Chemical Society
Issue number35
Publication statusPublished - 2007

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