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New light on an old debate: does the RCN–PtCl2 bond include any back-donation? RCN←PtCl2 backbonding vs. the IR νC[triple bond, length as m-dash]N blue-shift dichotomy in organonitriles–platinum(II) complexes. A thorough density functional theory – energy decomposition analysis study

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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).

Graphical abstract: New light on an old debate: does the RCN–PtCl2 bond include any back-donation? RCN←PtCl2 backbonding vs. the IR νC [[triple bond, length as m-dash]] N blue-shift dichotomy in organonitriles–platinum(ii) complexes. A thorough density functional theory – energy decomposition analysis study

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Publication details

The article was received on 08 Jun 2019, accepted on 31 Jul 2019 and first published on 01 Aug 2019


Article type: Paper
DOI: 10.1039/C9DT02440A
Dalton Trans., 2019, Advance Article

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    New light on an old debate: does the RCN–PtCl2 bond include any back-donation? RCN←PtCl2 backbonding vs. the IR νC[triple bond, length as m-dash]N blue-shift dichotomy in organonitriles–platinum(II) complexes. A thorough density functional theory – energy decomposition analysis study

    G. Casella, C. Fonseca Guerra, S. Carlotto, P. Sgarbossa, R. Bertani and M. Casarin, Dalton Trans., 2019, Advance Article , DOI: 10.1039/C9DT02440A

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