Theoretical studies of multiple bonds in gallium–gallium and germanium–germanium compounds †

Allen, Thomas L.; Fink, William H.; Power, Philip P.

doi:10.1039/a907421j

Cited by 76 publications

(71 citation statements)

References 39 publications

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“…[39] These conclusions are also consistent with previous independent calculations from several groups [18,22,[24][25][26][27] who have concluded that the Ga À Ga bond in the corresponding doubly reduced Na 2 [Ar*GaGaAr*] and various related model species is relatively weak. The Na 2 A C H T U N G T R E N N U N G [ArGaGaAr] units may be regarded as a cluster species in which the weak Ga À Ga bond is shortened by a number of factors including Na + À aryl and Na-Ga-Na interactions.…”

Section: Resultssupporting

confidence: 90%

“…This description led to a lively debate [17][18][19][20][21][22][23][24][25][26][27][28][29] in which several groups advanced the view that the Ga À Ga bond order was considerably lower on the basis of computational and structural considerations. [18,22,26] However, there are very few experimental studies available that might throw further light on the nature of the GaÀGa bonding. We have previously shown [30,31] that the use of the slightly less bulky Ar' (Ar' = C 6 H 3 -2,6(C 6 H 3 -2,6-iPr 2 ) 2 ) substituent yielded Na 2 [Ar'GaGaAr'], which had a very similar structure to that of that of Na 2 [Ar*GaGaAr*].…”

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confidence: 99%

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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

Fischer

Ellis

et al. 2009

Chemistry A European J

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A series of stable aryl gallium(I) terphenyl derivatives was synthesized and characterized spectroscopically, structurally and by density functional calculations. Dimeric structures with trans-bent planar CGaGaC core arrangements were observed for [(GaAr*-4-tBu)(2)] (7, Ar*-4-tBu = C(6)H(2)-2,6(C(6)H(2)-2,4,6-iPr(3))(2)-4-tBu) and [(GaAr*-4-CF(3))(2)] (8, Ar*-4-CF(3) = C(6)H(2)-2,6(C(6)H(2)-2,4,6-iPr(3))(2)-4-CF(3)), whereas monomeric structures featuring one coordinate gallium were observed for the more crowded complexes [:GaAr*-3,5-iPr(2)] (10, Ar*-3,5-iPr(2) = C(6)H-2,6(C(6)H(2)-2,4-6-iPr(3))(2)-3,5-iPr(2)) and [GaAr'-3,5-iPr(2)] (11, Ar'-3,5-iPr(2) = C(6)H-2,6(C(6)H(3)-2,6-iPr(2))(2)-3,5-iPr(2)). Complexes 7 and 8 dissociate to monomers in hydrocarbon solution and their electronic spectra closely resemble those of 10 and 11 as well as those of [Ar'GaGaAr'] (Ar' = C(6)H(3)-2,6(C(6)H(3)-2,6-iPr(3))(2)) and [(GaAr*)(n)] (Ar* = C(6)H(3)-2,6(C(6)H(2)-2,4,6-iPr(3))(2)). The calculations showed that the binding energies of the compounds are weak, resemble closed-shell interactions and average approximately 5 kcal mol(-1), as in [Ar*GaGaAr*] with a lowest value of approximately -2 kcal mol(-1) for monomeric 10 and a highest value approximately 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 Na(2)[Ar*GaGaAr*] and Na(2)[Ar'GaGaAr'] is also weak and is consistent with approximate single bonding.

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Section: Resultssupporting

confidence: 90%

mentioning

confidence: 99%

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

Fischer

Ellis

et al. 2009

Chemistry A European J

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“…This is, for example, the case of the bonds between the elements of the 13 and 14 group of the periodic table (Ga, Ge, Sn, Pb). [7][8][9][10][11][12][13][14] Nontrivial and controversial bonding patterns have also been dealt with in our recent studies based on the analysis of the so-called domain-averaged Fermi holes. [15][16][17][18][19] In view of the success of this new theoretical methodology in the description and visualization of the complicated bonding patterns, we decided to also apply it to the scrutiny of another widely discussed metalmetal bond whose nature is still not completely understood, namely the Mn-Mn bond in the bis(pentacarbonylmanganese).…”

Section: Introductionmentioning

confidence: 99%

Chemical structures from the analysis of domain‐averaged fermi holes. Nature of the MnMn bond in bis(pentacarbonylmanganese)

2005

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Abstract:Because of conflicting and contradictory classification based on traditional AIM characteristics, the nature of the Mn-Mn bond has been and still is the subject of continuing discussions. To overcome the existing inconsistencies in the interpretation of the nature of this bond, the bonding in Mn 2 (CO) 10 has been analyzed and discussed in terms of new recently proposed methodology known as the analysis of domain-averaged Fermi holes. It has been shown that this analysis is able to reconcile the conflicting conclusions of earlier AIM-based studies with traditional anticipations based on simple electron counting rules. According to Fermi hole analysis, the Mn-Mn bond has the character of the more or less ordinary covalent single bond, but the analysis also brings clear evidence in favor of Mn ⅐ ⅐ ⅐ (CO) intramolecular interactions between the metal atom and the ligands bonded to the other metal atom. These interactions could be responsible for the observed decrease of electron density at the bond critical point detected in AIM studies.

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“…The works of Klinkhammer [1] and of others [7,8] who considered the question of the multiplicity of the Ga-Ga interaction, use diering de®nitions of localized molecular orbitals in their interpretation and consequently reach dierent and uncertain conclusions to a problem that has a unique physical answer. More recently, Allen et al [9] have presented an analysis of the bonding in the dianion that``rests primarily on the nature of the canonical molecular orbitals'', providing as well, a comparison with and a critical assessment of the other orbital interpretations.…”

Section: Introductionmentioning

confidence: 99%

Recognizing a triple bond between main group atoms

Molina

Dobado

Heard

et al. 2001

Theoretical Chemistry Accounts: Theory, Computation, and Modeli

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The electron pair density, in conjunction with the theory of an atom in a molecule, enables one to unambiguously determine the nature of the bonding between the gallium atoms in bent [HGa-GaH] 2) . The Ga-Ga bonding in the dianion at the experimental bond length is found to be the result of the sharing of two electron pairs at the Hartree-Fock level of theory, the level consistent with the Lewis model of the electron pair.

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Theoretical studies of multiple bonds in gallium–gallium and germanium–germanium compounds †

Cited by 76 publications

References 39 publications

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

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

Chemical structures from the analysis of domain‐averaged fermi holes. Nature of the MnMn bond in bis(pentacarbonylmanganese)

Recognizing a triple bond between main group atoms

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