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Theoretical versus experimental charge and spin-density distributions in trans-[Ni(NH3)4(NO2)2]
Journal article   Open access   Peer reviewed

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. Phillips
Journal of the Chemical Society - Dalton Transactions, (4), pp.1417-1427
1990
DOI: https://doi.org/10.1039/DT9900001417
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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 13Fock (UHF) and discrete variational X;1(DVX;1) Hartree 13Fock 13Slater molecular orbital (m.o.) calculations are reported together with cellular ligand field (c.l.f.) results. The UHF and DVX;1 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 13N covalence is strong, the NO2 13 ion is a better <3 donor than the NH3 molecule, and the Ni 13N <0-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 13N interactions reproduce the experimental d 13d spectra and the signs of the single-crystal paramagnetic anisotropies quite well, but assign a weaker <3-donor role to the nitrite ligand relative to NH3. An extension of the model to include explicit Ni 13O interactions is more satisfactory and places the NO2 13 ion as the stronger <3 donor consistent with the other theoretical and experimental data.

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