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Aullón G, Crespo M, Font-Bardia M, et al. A combined kinetico-mechanistic and computational study on the competitive formation of seven- versus five-membered platinacycles; the relevance of spectator halide ligands. Dalton Trans. 2015;44(41):17968-79doi: 10.1039/c5dt02657a.
Aullón, G., Crespo, M., Font-Bardia, M., Jover, J., Martínez, M., & Pike, J. (2015). A combined kinetico-mechanistic and computational study on the competitive formation of seven- versus five-membered platinacycles; the relevance of spectator halide ligands. Dalton transactions (Cambridge, England : 2003), 44(41), 17968-79. https://doi.org/10.1039/c5dt02657a
Aullón, Gabriel, et al. "A combined kinetico-mechanistic and computational study on the competitive formation of seven- versus five-membered platinacycles; the relevance of spectator halide ligands." Dalton transactions (Cambridge, England : 2003) vol. 44,41 (2015): 17968-79. doi: https://doi.org/10.1039/c5dt02657a
Aullón G, Crespo M, Font-Bardia M, Jover J, Martínez M, Pike J. A combined kinetico-mechanistic and computational study on the competitive formation of seven- versus five-membered platinacycles; the relevance of spectator halide ligands. Dalton Trans. 2015 Nov 07;44(41):17968-79. doi: 10.1039/c5dt02657a. Epub 2015 Sep 24. PMID: 26399622.
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Dalton Trans. 2015 Nov 07;44(41):17968-79. doi: 10.1039/c5dt02657a. Epub 2015 Sep 24.

A combined kinetico-mechanistic and computational study on the competitive formation of seven- versus five-membered platinacycles; the relevance of spectator halide ligands.

Dalton transactions (Cambridge, England : 2003)

Gabriel Aullón, Margarita Crespo, Mercè Font-Bardia, Jesús Jover, Manuel Martínez, Jack Pike

Affiliations

  1. Departament de Química Inorgànica, Universitat de Barcelona, Martí i Franquès 1-11, E-08028 Barcelona, Spain. [email protected] [email protected].

PMID: 26399622 DOI: 10.1039/c5dt02657a

Abstract

The metalation reactions between [Pt2(4-MeC6H4)4(μ-SEt2)2] and 2-X,6-FC6H3CH[double bond, length as m-dash]NCH2CH2NMe2 (X = Br, Cl) have been studied. In all cases, seven-membered platinacycles are formed in a process that involves an initial reductive elimination from cyclometallated Pt(IV) intermediate compounds, [PtX(4-CH3C6H4)2(ArCH[double bond, length as m-dash]NCH2CH2NMe2)] (X = Br, Cl), followed by isomerization of the resulting Pt(II) complexes and a final cyclometallation step. For the process with X = Br, the final seven-membered platinacycle and two intermediates, isolated under the conditions implemented from parallel kinetic studies, have been characterized by XRD. Contrary to previous results for the parent non-fluorinated imine 2-BrC6H4CH[double bond, length as m-dash]NCH2CH2NMe2 the presence of a fluoro substituent prevents the formation of the more stable five-membered platinacycle. Temperature and pressure dependent kinetico-mechanistic and DFT studies indicate that the final cyclometallation step is strongly influenced by the nature of the spectator halido ligand, the overall reaction being much faster for X = Cl. The same DFT study conducted on the previously studied systems with imine 2-BrC6H4CH[double bond, length as m-dash]NCH2CH2NMe2 indicates that, when possible, five-membered platinacycles are kinetically preferred for X = Br, while the presence of Cl as a spectator halido ligand leads to a preferential faster formation of seven-membered analogues.

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