A NMR, X-ray, and DFT combined study on the regio-chemistry of nucleophilic addition to platinium(II) coordinated terminal olefins
| Autor: | Luciana Maresca, Carmen R. Barone, Gabriella Tamasi, Eric Clot, Renzo Cini, Giovanni Natile, Odile Eisenstein |
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| Přispěvatelé: | Dipartimento Farmaco-Chimico, Università degli studi di Bari Aldo Moro (UNIBA), Dipartamento di Scienze e Tecnologie Chimiche e dei Biosistemi, Università degli Studi di Siena = University of Siena (UNISI), Institut Charles Gerhardt Montpellier - Institut de Chimie Moléculaire et des Matériaux de Montpellier (ICGM ICMMM), Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Centre National de la Recherche Scientifique (CNRS)-Université de Montpellier (UM)-Université Montpellier 1 (UM1)-Université Montpellier 2 - Sciences et Techniques (UM2)-Institut de Chimie du CNRS (INC) |
| Jazyk: | angličtina |
| Rok vydání: | 2008 |
| Předmět: |
arenes
Stereochemistry Markovnikov's rule chemistry.chemical_element Electron donor 010402 general chemistry 01 natural sciences Biochemistry Medicinal chemistry Inorganic Chemistry chemistry.chemical_compound NMR spectroscopy Nucleophile Materials Chemistry platinum X-ray diffraction density functional calculations Physical and Theoretical Chemistry Nucleophilic addition 010405 organic chemistry Chemistry Organic Chemistry Nuclear magnetic resonance spectroscopy 0104 chemical sciences Bond length Polar effect [PHYS.PHYS.PHYS-CHEM-PH]Physics [physics]/Physics [physics]/Chemical Physics [physics.chem-ph] Platinum |
| Zdroj: | Journal of Organometallic Chemistry Journal of Organometallic Chemistry, Elsevier, 2008, 693, pp.2819. ⟨10.1016/j.jorganchem.2008.05.040⟩ |
| ISSN: | 0022-328X |
| DOI: | 10.1016/j.jorganchem.2008.05.040⟩ |
| Popis: | The series of platinum complexes [PtCl(η 2 -CH 2 CH–C 6 H 4 –X)(tmeda)](ClO 4 ) (X = H, 1b ; 4-OMe, 1c ; 3-OMe, 1d ; 4-CF 3 , 1e ; 3-CF 3 , 1f ; 3-NO 2 , 1g ; tmeda = N , N , N ′, N ′-tetramethyl-1,2-ethanediamine) has been considered. In the styrene complex ( 1b ) both solution (NMR) and solid state (X-ray) data indicate a significant difference in the Pt–C bond lengths (the longer bond being that involving the olefin carbon atom carrying the phenyl ring). Such a difference increases when X is an electron donor group (EDG, 1c ) and decreases when X is an electron withdrawing group (EWG, 1d – g ). The attack of a nucleophile (MeO − ) to the substituted carbon (Markovnikov type, M) is by far the most favoured in the case of unsubstituted ( 1b ) or EDG-substituted ( 1c ) styrenes. The presence of an EWG (compounds 1d - g ) levels off the probability of M and anti -M type of attack. DFT calculations on 1b , c and 1e were also performed. The NLMO analysis reveals the crucial role of the interaction between the filled π orbital of the olefin and the empty d orbital of platinum; the carbon with greater electron density becoming less susceptible of nucleophilic attack. |
| Databáze: | OpenAIRE |
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