Your browser doesn't support javascript.
loading
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.
Casella, Girolamo; Fonseca Guerra, Célia; Carlotto, Silvia; Sgarbossa, Paolo; Bertani, Roberta; Casarin, Maurizio.
Afiliação
  • Casella G; Dipartimento di Scienze della Terra e del Mare, Università degli Studi di Palermo, Via Archirafi, 22, 90123 Palermo, Italy. girolamo.casella@unipa.it and Consorzio Interuniversitario di Ricerca in Chimica dei Metalli nei Sistemi Biologici (C.I.R.C.M.S.B.) - Piazza Umberto I, 70121 Bari, Italy.
  • Fonseca Guerra C; Department of Theoretical Chemistry and Amsterdam Center for Multiscale Modeling, Vrije Universiteit Amsterdam, De Boelelaan 1083, 1081 HV Amsterdam, The Netherlands and Leiden Institute of Chemistry, Gorlaeus Laboratories, Leiden University, Einsteinweg 55, 2333 CC Leiden, The Netherlands.
  • Carlotto S; Dipartimento di Scienze Chimiche, Università degli Studi di Padova, via F. Marzolo 1, 35131 Padova, Italy.
  • Sgarbossa P; Dipartimento di Ingegneria Industriale, Università degli Studi di Padova, via F. Marzolo 9, 35131 Padova, Italy.
  • Bertani R; Dipartimento di Ingegneria Industriale, Università degli Studi di Padova, via F. Marzolo 9, 35131 Padova, Italy.
  • Casarin M; Dipartimento di Scienze Chimiche, Università degli Studi di Padova, via F. Marzolo 1, 35131 Padova, Italy.
Dalton Trans ; 48(34): 12974-12985, 2019 Sep 14.
Artigo em Inglês | MEDLINE | ID: mdl-31397469
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).

Similares

MEDLINE

...
LILACS

LIS

Texto completo: Disponível Coleções: Bases de dados internacionais Base de dados: MEDLINE Idioma: Inglês Revista: Dalton Trans Assunto da revista: Química Ano de publicação: 2019 Tipo de documento: Artigo País de afiliação: Itália