Abstract
For a series of organonitrile [RCN (R = Me, CF3, Ph, CH3Ph, CF3Ph)] ligands, the nature of the N-Pt bond in the related cis-/trans-(RCN)2PtCl2 complexes has been computationally investigated by Density Functional Theory. A fragment based bond analysis has been performed in the canonical Kohn-Sham molecular orbitals framework, and it has been ultimately assessed that this bond is characterized both by N→Pt σ and by N←Pt π contributions. Voronoi Deformation Density charges further confirms the occurrence of N←Pt π interactions. Moreover, the Energy Decomposition Analysis-Natural Orbital for Chemical Valence (EDA-NOCV) method shows that the strength of the N←Pt π interaction is not negligible by contributing to about 30-40% of the total orbital interaction. Finally, the well-known νC[triple bond, length as m-dash]N blue-shift occurring upon coordination to PtII, has been thoroughly investigated by exploiting the EDA-NOCV and by evaluating νC[triple bond, length as m-dash]N and force constants. The origin of the νC[triple bond, length as m-dash]N blue-shift in these systems has been discussed on the basis of the CN bond polarization. N←Pt π backbonding causes only a systematic decrease of the observed νC[triple bond, length as m-dash]N blue-shift when compared to the one calculated for RCN-X (X = H+, alkaline, Lewis acids) herein reported (X = purely σ acceptors).
Highlights
Correction: New light on an old debate: does the RCN–PtCl2 bond include any back-donation? RCN ← PtCl2 backbonding vs. the IR νCuN blue-shift dichotomy in organonitriles–platinum(II) complexes
Correction for ‘New light on an old debate: does the RCN–PtCl2 bond include any back-donation? RCN ← PtCl2 backbonding vs. the IR νCuN blue-shift dichotomy in organonitriles–platinum(II) complexes
Corrigendum “The explanation of this behavior based solely on the σ/π donation/backdonation orbital interaction model discussed earlier, would imply the lack of any N ← Pt π back-donation, or at least the occurrence of such interaction which cannot overcome the effect of the N → Pt σ donation”.6b (iii) In the “EDA_NOCV analysis” section Erratum “The results are given in Table 4 and indicate that the total N ← Pt π back-donation represents about 30% of the total ΔEOrb term and ranges from 32% to 37% with respect to the N → Pt σ interaction which means that the orbital interaction...”
Summary
Correction: New light on an old debate: does the RCN–PtCl2 bond include any back-donation? RCN ← PtCl2 backbonding vs. the IR νCuN blue-shift dichotomy in organonitriles–platinum(II) complexes. Cite this: Dalton Trans., 2019, 48, 13491
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