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

Research output: Contribution to journalArticleResearchpeer-review

Abstract

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
Volume129
Issue number35
DOIs
Publication statusPublished - 2007

Keywords

    Cite this

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

    In: Journal of the American Chemical Society, Vol. 129, No. 35, 2007, p. 10847-10857.

    Research output: Contribution to journalArticleResearchpeer-review

    Zhu, Zhongliang ; Brynda, Marcin ; Wright, Robert J. ; Fischer, Roland C. ; Merrill, W. Alexander ; Rivard, Eric ; Wolf, Robert ; Fettinger, James C. ; Olmstead, Marilyn M. ; Power, Philip P. / 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. In: Journal of the American Chemical Society. 2007 ; Vol. 129, No. 35. pp. 10847-10857.
    @article{3fe764177cf74f62af3fec0521f2c7fa,
    title = "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.",
    abstract = "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) {\AA} 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)]",
    keywords = "zinc cadmium mercury aryl halide hydride prepn crystal structure, crystal mol structure zinc cadmium mercury aryl halide hydride",
    author = "Zhongliang Zhu and Marcin Brynda and Wright, {Robert J.} and Fischer, {Roland C.} and Merrill, {W. Alexander} and Eric Rivard and Robert Wolf and Fettinger, {James C.} and Olmstead, {Marilyn M.} and Power, {Philip P.}",
    note = "M1 - Copyright (C) 2017 American Chemical Society (ACS). All Rights Reserved. CAPLUS AN 2007:899567(Journal)",
    year = "2007",
    doi = "10.1021/ja072682x",
    language = "English",
    volume = "129",
    pages = "10847--10857",
    journal = "Journal of the American Chemical Society",
    issn = "0002-7863",
    publisher = "American Chemical Society",
    number = "35",

    }

    TY - JOUR

    T1 - 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.

    AU - Zhu, Zhongliang

    AU - Brynda, Marcin

    AU - Wright, Robert J.

    AU - Fischer, Roland C.

    AU - Merrill, W. Alexander

    AU - Rivard, Eric

    AU - Wolf, Robert

    AU - Fettinger, James C.

    AU - Olmstead, Marilyn M.

    AU - Power, Philip P.

    N1 - M1 - Copyright (C) 2017 American Chemical Society (ACS). All Rights Reserved. CAPLUS AN 2007:899567(Journal)

    PY - 2007

    Y1 - 2007

    N2 - 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)]

    AB - 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)]

    KW - zinc cadmium mercury aryl halide hydride prepn crystal structure

    KW - crystal mol structure zinc cadmium mercury aryl halide hydride

    U2 - 10.1021/ja072682x

    DO - 10.1021/ja072682x

    M3 - Article

    VL - 129

    SP - 10847

    EP - 10857

    JO - Journal of the American Chemical Society

    JF - Journal of the American Chemical Society

    SN - 0002-7863

    IS - 35

    ER -