Academic Journal
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
| العنوان: | 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 |
|---|---|
| المؤلفون: | Casella, Girolamo, Fonseca Guerra, Célia, Carlotto, Silvia, Sgarbossa, Paolo, Bertani, Roberta, Casarin, Maurizio |
| المصدر: | 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 , vol. 48 , no. 34 , pp. 12974-12985 . https://doi.org/10.1039/c9dt02440a |
| سنة النشر: | 2019 |
| مصطلحات موضوعية: | /dk/atira/pure/sustainabledevelopmentgoals/affordable_and_clean_energy, name=SDG 7 - Affordable and Clean Energy |
| الوصف: | For a series of organonitrile [RCN (R = Me, CF 3 , Ph, CH 3 Ph, CF 3 Ph)] ligands, the nature of the N-Pt bond in the related cis-/trans-(RCN) 2 PtCl 2 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 ν CN blue-shift occurring upon coordination to Pt II , has been thoroughly investigated by exploiting the EDA-NOCV and by evaluating ν CN and force constants. The origin of the ν CN 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 ν CN blue-shift when compared to the one calculated for RCN-X (X = H + , alkaline, Lewis acids) herein reported (X = purely σ acceptors). |
| نوع الوثيقة: | article in journal/newspaper |
| وصف الملف: | application/pdf |
| اللغة: | English |
| DOI: | 10.1039/c9dt02440a |
| الاتاحة: | https://research.vu.nl/en/publications/856e7162-3063-483e-8e30-59b519c8120e https://doi.org/10.1039/c9dt02440a https://hdl.handle.net/1871.1/856e7162-3063-483e-8e30-59b519c8120e https://research.vu.nl/ws/files/236741607/New_light_on_an_old_debate.pdf http://www.scopus.com/inward/record.url?scp=85071680589&partnerID=8YFLogxK http://www.scopus.com/inward/citedby.url?scp=85071680589&partnerID=8YFLogxK |
| Rights: | info:eu-repo/semantics/openAccess |
| رقم الانضمام: | edsbas.CC54B37A |
| قاعدة البيانات: | BASE |
| DOI: | 10.1039/c9dt02440a |
|---|