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 νCN blue-shift occurring upon coordination to PtII, has been thoroughly investigated by exploiting the EDA-NOCV and by evaluating νCN and force constants. The origin of the νCN 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 νCN blue-shift when compared to the one calculated for RCN-X (X = H+, alkaline, Lewis acids) herein reported (X = purely σ acceptors).

Casella G., Fonseca Guerra C., Carlotto S., Sgarbossa P., Bertani R., Casarin M. (2019). New light on an old debate: Does the RCN-PtCl2 bond include any back-donation? RCN←PtCl2 backbonding: Vs. the IR ν CN blue-shift dichotomy in organonitriles-platinum(II) complexes. A thorough density functional theory-energy decomposition analysis study. DALTON TRANSACTIONS, 48(34), 12974-12985 [10.1039/c9dt02440a].

New light on an old debate: Does the RCN-PtCl2 bond include any back-donation? RCN←PtCl2 backbonding: Vs. the IR ν CN blue-shift dichotomy in organonitriles-platinum(II) complexes. A thorough density functional theory-energy decomposition analysis study

Casella, Girolamo
;
2019-01-01

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 νCN blue-shift occurring upon coordination to PtII, has been thoroughly investigated by exploiting the EDA-NOCV and by evaluating νCN and force constants. The origin of the νCN 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 νCN blue-shift when compared to the one calculated for RCN-X (X = H+, alkaline, Lewis acids) herein reported (X = purely σ acceptors).
Settore CHIM/03 - Chimica Generale E Inorganica
https://pubs.rsc.org/en/content/articlelanding/2019/dt/c9dt02440a#!divAbstract
Casella G., Fonseca Guerra C., Carlotto S., Sgarbossa P., Bertani R., Casarin M. (2019). New light on an old debate: Does the RCN-PtCl2 bond include any back-donation? RCN←PtCl2 backbonding: Vs. the IR ν CN blue-shift dichotomy in organonitriles-platinum(II) complexes. A thorough density functional theory-energy decomposition analysis study. DALTON TRANSACTIONS, 48(34), 12974-12985 [10.1039/c9dt02440a].
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Utilizza questo identificativo per citare o creare un link a questo documento: https://hdl.handle.net/10447/367282
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