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Issue 22, 2003
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The length, strength and polarity of metal–carbon bonds: dialkylzinc compounds studied by density functional theory calculations, gas electron diffraction and photoelectron spectroscopy

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Abstract

The molecular structures and thermodynamic functions of seven dialkyl zinc compounds, R2Zn, R = Me, Et, i-Pr, t-Bu, n-Pr, neopentyl and the silaneopentyl Me3SiCH2, of the parent hydrocarbons RH and of the radicals R have been determined by density functional theory calculations at the B3LYP/SDD level. The molecular structures of the i-Pr, t-Bu, neo-Pe and Me3SiCH2 derivatives have been determined by gas electron diffraction. Me2Zn, Et2Zn, t-Bu2Zn and neo-Pe2Zn have been studied by photoelectron spectroscopy and the ionisation energies calculated. Both experimental and calculated Zn-C bond distances were found to increase in the order Me2Zn ≈ (Me3SiCH2)2Zn < Et2Zn ≈ n-Pr2Zn ≈ neo-Pe2Zn < i-Pr2Zn < t-Bu2Zn.

Calculated mean bond rupture enthalpies indicate that the strength of the Zn–C bonds decrease in the same order, viz. Me2Zn ≈ (Me3SiCH2)2Zn > Et2Zn ≈ n-Pr2Zn ≈ neo-Pe2Zn > i-Pr2Zn > t-Bu2Zn.

Both bond lengths and bond strengths were found to be strongly correlated with the inductive Taft constant I, indicating that the bond strength increases and the bond length decreases with increasing electron withdrawing power of the alkyl group. Evidence from the literature indicates that bond strengths and bond lengths in homoleptic alkyl derivatives of the main group metals in Groups 12, 13 and 14 and of the transition elements in Group 4 vary in the same manner.

Graphical abstract: The length, strength and polarity of metal–carbon bonds: dialkylzinc compounds studied by density functional theory calculations, gas electron diffraction and photoelectron spectroscopy

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Publication details

The article was received on 16 Jun 2003, accepted on 02 Sep 2003 and first published on 19 Sep 2003


Article type: Paper
DOI: 10.1039/B306840B
Citation: Dalton Trans., 2003, 4356-4366
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    The length, strength and polarity of metal–carbon bonds: dialkylzinc compounds studied by density functional theory calculations, gas electron diffraction and photoelectron spectroscopy

    A. Haaland, J. C. Green, G. S. McGrady, A. J. Downs, E. Gullo, M. J. Lyall, J. Timberlake, A. V. Tutukin, H. V. Volden and K. Østby, Dalton Trans., 2003, 4356
    DOI: 10.1039/B306840B

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