Substitution reactions on cyclometalated Pt(IV) complexes. Associative tuning by fluoro ligands and fluorinated substituents

Inorganic Chemistry
P V BernhardtTeodor Parella

Abstract

The substitution reactions of sulfide by phosphines on Pt(IV) complexes having a cyclometalated imine ligand, two methyl groups in a cis geometrical arrangement, and a halogen and a sulfide as ligands, [Pt (Me)(2)X(C-N)(SR(2))], have been studied as a function of temperature, solvent, and electronic and steric characteristics of the phosphines, sulfides, X, and C-N. In most of these cases, a limiting dissociative mechanism has been found, where the dissociation of the sulfide ligand corresponds to the rate-determining step. The intermediate species formed behaves as a true pentacoordinated Pt(IV) compound in a steady-state concentration only for the systems with SMe(2); for the bulkier SEt(2) and SBzl(2) leaving ligands the rate constants and activation parameters show an important degree of solvent dependence, which correlates with the ability of the solvent to form hydrogen bonds. The X-ray crystal structure of one of the dibenzyl sulfide complexes has been determined, and the geometrical arrangement of the ligands has been determined by NOE NMR measurements at low temperature. The nature of the solvent, imine, sulfide, and halogen ligands produces differences in the reaction rates, which can be quantified very well by the co...Continue Reading

References

Nov 1, 1996·Journal of Magnetic Resonance. Series a·R Wagner, S Berger
Jan 1, 1997·Journal of Magnetic Resonance·M J GradwellT A Frenkiel

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Citations

Nov 3, 2012·Inorganic Chemistry·Paul V BernhardtCarlos Rodríguez
Jul 15, 2015·Dalton Transactions : an International Journal of Inorganic Chemistry·Margarita CrespoManuel Martínez
Oct 1, 2009·Dalton Transactions : an International Journal of Inorganic Chemistry·Gabriel AullónXavier Solans
Nov 16, 2010·Chemistry : a European Journal·Inmaculada AngurellMarianne Engeser
Dec 18, 2004·Dalton Transactions : an International Journal of Inorganic Chemistry·Isabelle FavierMerce Font-Bardia
Feb 8, 2011·Dalton Transactions : an International Journal of Inorganic Chemistry·Julio Esteban, Manuel Martínez
Dec 31, 2010·Inorganic Chemistry·Paul V BernhardtMarta Vazquez

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