Synthesis, Characterization and Real Molecule DFT Calculations for Neutral Organogallium(I) Aryl Dimers and Monomers: Weakness of Gallium-Gallium Bonds in Digallenes and Digallynes.

Zhongliang Zhu, Roland C. Fischer, Bobby D. Ellis, Eric Rivard, W. Alexander Merrill, Marilyn M. Olmstead, Philip P. Power, J. D. Guo, Shigeru Nagase, Lihung. Pu

Research output: Contribution to journalArticleResearchpeer-review

Abstract

A series of stable aryl gallium(I) terphenyl derivs. was synthesized and characterized spectroscopically, structurally and by d. functional calcns. Dimeric structures with trans-bent planar CGaGaC core arrangements were obsd. for [(GaAr*-4-tBu)2] (7, Ar*-4-tBu = C6H2-2,6(C6H2-2,4,6-iPr3)2-4-tBu) and [(GaAr*-4-CF3)2] (8, Ar*-4-CF3 = C6H2-2,6(C6H2-2,4,6-iPr3)2-4-CF3), whereas monomeric structures featuring one coordinate gallium were obsd. for the more crowded complexes [:GaAr*-3,5-iPr2] (10, Ar*-3,5-iPr2 = C6H-2,6(C6H2-2,4-6-iPr3)2-3,5-iPr2) and [GaAr'-3,5-iPr2] (11, Ar'-3,5-iPr2 = C6H-2,6(C6H3-2,6-iPr2)2-3,5-iPr2). Complexes 7 and 8 dissoc. to monomers in hydrocarbon soln. and their electronic spectra closely resemble those of 10 and 11 as well as those of [Ar'GaGaAr'] (Ar' = C6H3-2,6(C6H3-2,6-iPr3)2) and [(GaAr*)n] (Ar* = C6H3-2,6(C6H2-2,4,6-iPr3)2). The calcns. showed that the binding energies of the compds. are weak, resemble closed-shell interactions and av. ≈5 kcal mol-1, as in [Ar*GaGaAr*] with a lowest value of ≈-2 kcal mol-1 for monomeric 10 and a highest value ≈9 kcal mol-1 for the least crowded species [Ar'GaGaAr']. The weak bonding in the complexes supports the view that the GaGa bonding in the previously published doubly reduced Na2[Ar*GaGaAr*] and Na2[Ar'GaGaAr'] is also weak and is consistent with approx. single bonding. [on SciFinder(R)]
Original languageEnglish
Pages (from-to)5263-5272
Number of pages10
JournalChemistry - a European Journal
Volume15
Issue number21
DOIs
Publication statusPublished - 2009

Keywords

    Cite this

    Synthesis, Characterization and Real Molecule DFT Calculations for Neutral Organogallium(I) Aryl Dimers and Monomers: Weakness of Gallium-Gallium Bonds in Digallenes and Digallynes. / Zhu, Zhongliang; Fischer, Roland C.; Ellis, Bobby D.; Rivard, Eric; Merrill, W. Alexander; Olmstead, Marilyn M.; Power, Philip P.; Guo, J. D.; Nagase, Shigeru; Pu, Lihung.

    In: Chemistry - a European Journal, Vol. 15, No. 21, 2009, p. 5263-5272.

    Research output: Contribution to journalArticleResearchpeer-review

    Zhu, Zhongliang ; Fischer, Roland C. ; Ellis, Bobby D. ; Rivard, Eric ; Merrill, W. Alexander ; Olmstead, Marilyn M. ; Power, Philip P. ; Guo, J. D. ; Nagase, Shigeru ; Pu, Lihung. / Synthesis, Characterization and Real Molecule DFT Calculations for Neutral Organogallium(I) Aryl Dimers and Monomers: Weakness of Gallium-Gallium Bonds in Digallenes and Digallynes. In: Chemistry - a European Journal. 2009 ; Vol. 15, No. 21. pp. 5263-5272.
    @article{8884f5b804344772944be89cadf0300b,
    title = "Synthesis, Characterization and Real Molecule DFT Calculations for Neutral Organogallium(I) Aryl Dimers and Monomers: Weakness of Gallium-Gallium Bonds in Digallenes and Digallynes.",
    abstract = "A series of stable aryl gallium(I) terphenyl derivs. was synthesized and characterized spectroscopically, structurally and by d. functional calcns. Dimeric structures with trans-bent planar CGaGaC core arrangements were obsd. for [(GaAr*-4-tBu)2] (7, Ar*-4-tBu = C6H2-2,6(C6H2-2,4,6-iPr3)2-4-tBu) and [(GaAr*-4-CF3)2] (8, Ar*-4-CF3 = C6H2-2,6(C6H2-2,4,6-iPr3)2-4-CF3), whereas monomeric structures featuring one coordinate gallium were obsd. for the more crowded complexes [:GaAr*-3,5-iPr2] (10, Ar*-3,5-iPr2 = C6H-2,6(C6H2-2,4-6-iPr3)2-3,5-iPr2) and [GaAr'-3,5-iPr2] (11, Ar'-3,5-iPr2 = C6H-2,6(C6H3-2,6-iPr2)2-3,5-iPr2). Complexes 7 and 8 dissoc. to monomers in hydrocarbon soln. and their electronic spectra closely resemble those of 10 and 11 as well as those of [Ar'GaGaAr'] (Ar' = C6H3-2,6(C6H3-2,6-iPr3)2) and [(GaAr*)n] (Ar* = C6H3-2,6(C6H2-2,4,6-iPr3)2). The calcns. showed that the binding energies of the compds. are weak, resemble closed-shell interactions and av. ≈5 kcal mol-1, as in [Ar*GaGaAr*] with a lowest value of ≈-2 kcal mol-1 for monomeric 10 and a highest value ≈9 kcal mol-1 for the least crowded species [Ar'GaGaAr']. The weak bonding in the complexes supports the view that the GaGa bonding in the previously published doubly reduced Na2[Ar*GaGaAr*] and Na2[Ar'GaGaAr'] is also weak and is consistent with approx. single bonding. [on SciFinder(R)]",
    keywords = "neutral arylgallium terphenyl dimer monomer prepn crystal mol structure, digallene digallyne prepn crystal mol structure",
    author = "Zhongliang Zhu and Fischer, {Roland C.} and Ellis, {Bobby D.} and Eric Rivard and Merrill, {W. Alexander} and Olmstead, {Marilyn M.} and Power, {Philip P.} and Guo, {J. D.} and Shigeru Nagase and Lihung. Pu",
    note = "M1 - Copyright (C) 2017 American Chemical Society (ACS). All Rights Reserved. CAPLUS AN 2009:606269(Journal)",
    year = "2009",
    doi = "10.1002/chem.200900201",
    language = "English",
    volume = "15",
    pages = "5263--5272",
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    TY - JOUR

    T1 - Synthesis, Characterization and Real Molecule DFT Calculations for Neutral Organogallium(I) Aryl Dimers and Monomers: Weakness of Gallium-Gallium Bonds in Digallenes and Digallynes.

    AU - Zhu, Zhongliang

    AU - Fischer, Roland C.

    AU - Ellis, Bobby D.

    AU - Rivard, Eric

    AU - Merrill, W. Alexander

    AU - Olmstead, Marilyn M.

    AU - Power, Philip P.

    AU - Guo, J. D.

    AU - Nagase, Shigeru

    AU - Pu, Lihung.

    N1 - M1 - Copyright (C) 2017 American Chemical Society (ACS). All Rights Reserved. CAPLUS AN 2009:606269(Journal)

    PY - 2009

    Y1 - 2009

    N2 - A series of stable aryl gallium(I) terphenyl derivs. was synthesized and characterized spectroscopically, structurally and by d. functional calcns. Dimeric structures with trans-bent planar CGaGaC core arrangements were obsd. for [(GaAr*-4-tBu)2] (7, Ar*-4-tBu = C6H2-2,6(C6H2-2,4,6-iPr3)2-4-tBu) and [(GaAr*-4-CF3)2] (8, Ar*-4-CF3 = C6H2-2,6(C6H2-2,4,6-iPr3)2-4-CF3), whereas monomeric structures featuring one coordinate gallium were obsd. for the more crowded complexes [:GaAr*-3,5-iPr2] (10, Ar*-3,5-iPr2 = C6H-2,6(C6H2-2,4-6-iPr3)2-3,5-iPr2) and [GaAr'-3,5-iPr2] (11, Ar'-3,5-iPr2 = C6H-2,6(C6H3-2,6-iPr2)2-3,5-iPr2). Complexes 7 and 8 dissoc. to monomers in hydrocarbon soln. and their electronic spectra closely resemble those of 10 and 11 as well as those of [Ar'GaGaAr'] (Ar' = C6H3-2,6(C6H3-2,6-iPr3)2) and [(GaAr*)n] (Ar* = C6H3-2,6(C6H2-2,4,6-iPr3)2). The calcns. showed that the binding energies of the compds. are weak, resemble closed-shell interactions and av. ≈5 kcal mol-1, as in [Ar*GaGaAr*] with a lowest value of ≈-2 kcal mol-1 for monomeric 10 and a highest value ≈9 kcal mol-1 for the least crowded species [Ar'GaGaAr']. The weak bonding in the complexes supports the view that the GaGa bonding in the previously published doubly reduced Na2[Ar*GaGaAr*] and Na2[Ar'GaGaAr'] is also weak and is consistent with approx. single bonding. [on SciFinder(R)]

    AB - A series of stable aryl gallium(I) terphenyl derivs. was synthesized and characterized spectroscopically, structurally and by d. functional calcns. Dimeric structures with trans-bent planar CGaGaC core arrangements were obsd. for [(GaAr*-4-tBu)2] (7, Ar*-4-tBu = C6H2-2,6(C6H2-2,4,6-iPr3)2-4-tBu) and [(GaAr*-4-CF3)2] (8, Ar*-4-CF3 = C6H2-2,6(C6H2-2,4,6-iPr3)2-4-CF3), whereas monomeric structures featuring one coordinate gallium were obsd. for the more crowded complexes [:GaAr*-3,5-iPr2] (10, Ar*-3,5-iPr2 = C6H-2,6(C6H2-2,4-6-iPr3)2-3,5-iPr2) and [GaAr'-3,5-iPr2] (11, Ar'-3,5-iPr2 = C6H-2,6(C6H3-2,6-iPr2)2-3,5-iPr2). Complexes 7 and 8 dissoc. to monomers in hydrocarbon soln. and their electronic spectra closely resemble those of 10 and 11 as well as those of [Ar'GaGaAr'] (Ar' = C6H3-2,6(C6H3-2,6-iPr3)2) and [(GaAr*)n] (Ar* = C6H3-2,6(C6H2-2,4,6-iPr3)2). The calcns. showed that the binding energies of the compds. are weak, resemble closed-shell interactions and av. ≈5 kcal mol-1, as in [Ar*GaGaAr*] with a lowest value of ≈-2 kcal mol-1 for monomeric 10 and a highest value ≈9 kcal mol-1 for the least crowded species [Ar'GaGaAr']. The weak bonding in the complexes supports the view that the GaGa bonding in the previously published doubly reduced Na2[Ar*GaGaAr*] and Na2[Ar'GaGaAr'] is also weak and is consistent with approx. single bonding. [on SciFinder(R)]

    KW - neutral arylgallium terphenyl dimer monomer prepn crystal mol structure

    KW - digallene digallyne prepn crystal mol structure

    U2 - 10.1002/chem.200900201

    DO - 10.1002/chem.200900201

    M3 - Article

    VL - 15

    SP - 5263

    EP - 5272

    JO - Chemistry - a European Journal

    JF - Chemistry - a European Journal

    SN - 0947-6539

    IS - 21

    ER -