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Issue 4, 1990
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Theoretical versus experimental charge and spin-density distributions in trans-[Ni(NH3)4(NO2)2]

Abstract

The experimental charge and spin-density distributions for [Ni(NH3)4(NO2)2] have been compared with theory at various levels. Ab initio unrestricted Hartree–Fock (UHF) and discrete variational Xα(DVXα) Hartree–Fock–Slater molecular orbital (m.o.) calculations are reported together with cellular ligand field (c.l.f.) results. The UHF and DVXα approaches yield closely similar descriptions of the charge and spin densities, and qualitatively reproduce the main features of both types of experimental data, namely the Ni–N covalence is strong, the NO2 ion is a better σ donor than the NH3 molecule, and the Ni–N π-bonding is small. Both theories indicate quite appreciable O(NO2) participation in the bonding and antibonding m.o.s involving nickel. C.l.f. calculations which include only the Ni–N interactions reproduce the experimental dd spectra and the signs of the single-crystal paramagnetic anisotropies quite well, but assign a weaker σ-donor role to the nitrite ligand relative to NH3. An extension of the model to include explicit Ni–O interactions is more satisfactory and places the NO2 ion as the stronger σ donor consistent with the other theoretical and experimental data.

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Article type: Paper
DOI: 10.1039/DT9900001417
Citation: J. Chem. Soc., Dalton Trans., 1990,0, 1417-1427
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    Theoretical versus experimental charge and spin-density distributions in trans-[Ni(NH3)4(NO2)2]

    G. S. Chandler, R. J. Deeth, B. N. Figgis and R. A. Phillips, J. Chem. Soc., Dalton Trans., 1990, 0, 1417
    DOI: 10.1039/DT9900001417

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