Cyclometalation reactions constitute one of the evergreen fields in synthetic chemistry because of the variety of applications, from substrate functionalization to catalyst production and model for C-H activation. A variation on this theme is rollover cyclometalation where a bidentate donor, such as 2,2'-bipyridine, upon C-H activation leads to a species with a free donor atom that is able to influence the properties, hence the reactivity, of the complex.We explored the similarities/differences between classical and rollover cyclometalation to check the importance of the second nitrogen donor by comparing suitably substituted 2,2'-bipyridines and 2-phenylpyridines; moreover the properties of the ligands were tuned to investigate the impact of stereoelectronic modification on the C-H activation process.The reactivity of the newly synthesized cyclometalates having formula [Pt(K2-NC)(CH3)(L)] (κ2-N,C = cyclometalated ligand, L = neutral ligand) was tested in different conditions: ligand substitutions, protonolysis, oxidative additions and reductive eliminations. A wide variety of mono and dinuclear complexes was obtained and fully characterized by NMR spectroscopy.Further insight has been sought fromin silicoexperiments using DFT calculations that led to a nice agreement with the chemistry observed.

Synthesis and reactivity of cycloplatinated rollover complexes, an experimental and theoretical approach / Maidich, Luca. - (2014 Jan 31).

Synthesis and reactivity of cycloplatinated rollover complexes, an experimental and theoretical approach

MAIDICH, Luca
2014-01-31

Abstract

Cyclometalation reactions constitute one of the evergreen fields in synthetic chemistry because of the variety of applications, from substrate functionalization to catalyst production and model for C-H activation. A variation on this theme is rollover cyclometalation where a bidentate donor, such as 2,2'-bipyridine, upon C-H activation leads to a species with a free donor atom that is able to influence the properties, hence the reactivity, of the complex.We explored the similarities/differences between classical and rollover cyclometalation to check the importance of the second nitrogen donor by comparing suitably substituted 2,2'-bipyridines and 2-phenylpyridines; moreover the properties of the ligands were tuned to investigate the impact of stereoelectronic modification on the C-H activation process.The reactivity of the newly synthesized cyclometalates having formula [Pt(K2-NC)(CH3)(L)] (κ2-N,C = cyclometalated ligand, L = neutral ligand) was tested in different conditions: ligand substitutions, protonolysis, oxidative additions and reductive eliminations. A wide variety of mono and dinuclear complexes was obtained and fully characterized by NMR spectroscopy.Further insight has been sought fromin silicoexperiments using DFT calculations that led to a nice agreement with the chemistry observed.
Cyclometalation; C-C coupling; DFT calculations; C-H activation; nitrogen ligands
Synthesis and reactivity of cycloplatinated rollover complexes, an experimental and theoretical approach / Maidich, Luca. - (2014 Jan 31).
File in questo prodotto:
File Dimensione Formato  
Maidich_L_Synthesis_reactivity_of_cycloplatinated.pdf

accesso aperto

Tipologia: Altro materiale allegato
Licenza: Non specificato
Dimensione 8.56 MB
Formato Adobe PDF
8.56 MB Adobe PDF Visualizza/Apri

I documenti in IRIS sono protetti da copyright e tutti i diritti sono riservati, salvo diversa indicazione.

Utilizza questo identificativo per citare o creare un link a questo documento: https://hdl.handle.net/11388/250833
Citazioni
  • ???jsp.display-item.citation.pmc??? ND
  • Scopus ND
  • ???jsp.display-item.citation.isi??? ND
social impact