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https://doi.org/10.5562/cca3344

Structure and Reactivity Relationships in Methyl and Hydrido Complexes of Platinum(II) by Group 15 Donor Atom Ligands

Stefanus Otto ; Department of Chemistry, University of the Free State, P.O. Box 339, Bloemfontein, 9300, South Africa
Ebrahiem Botha ; Department of Chemistry, University of the Free State, P.O. Box 339, Bloemfontein, 9300, South Africa
Andreas Roodt ; Department of Chemistry, University of the Free State, P.O. Box 339, Bloemfontein, 9300, South Africa

Puni tekst: engleski, pdf (4 MB) str. 265-279 preuzimanja: 345* citiraj
APA 6th Edition
Otto, S., Botha, E. i Roodt, A. (2018). Structure and Reactivity Relationships in Methyl and Hydrido Complexes of Platinum(II) by Group 15 Donor Atom Ligands. Croatica Chemica Acta, 91 (2), 265-279. https://doi.org/10.5562/cca3344
MLA 8th Edition
Otto, Stefanus, et al. "Structure and Reactivity Relationships in Methyl and Hydrido Complexes of Platinum(II) by Group 15 Donor Atom Ligands." Croatica Chemica Acta, vol. 91, br. 2, 2018, str. 265-279. https://doi.org/10.5562/cca3344. Citirano 05.03.2021.
Chicago 17th Edition
Otto, Stefanus, Ebrahiem Botha i Andreas Roodt. "Structure and Reactivity Relationships in Methyl and Hydrido Complexes of Platinum(II) by Group 15 Donor Atom Ligands." Croatica Chemica Acta 91, br. 2 (2018): 265-279. https://doi.org/10.5562/cca3344
Harvard
Otto, S., Botha, E., i Roodt, A. (2018). 'Structure and Reactivity Relationships in Methyl and Hydrido Complexes of Platinum(II) by Group 15 Donor Atom Ligands', Croatica Chemica Acta, 91(2), str. 265-279. https://doi.org/10.5562/cca3344
Vancouver
Otto S, Botha E, Roodt A. Structure and Reactivity Relationships in Methyl and Hydrido Complexes of Platinum(II) by Group 15 Donor Atom Ligands. Croatica Chemica Acta [Internet]. 2018 [pristupljeno 05.03.2021.];91(2):265-279. https://doi.org/10.5562/cca3344
IEEE
S. Otto, E. Botha i A. Roodt, "Structure and Reactivity Relationships in Methyl and Hydrido Complexes of Platinum(II) by Group 15 Donor Atom Ligands", Croatica Chemica Acta, vol.91, br. 2, str. 265-279, 2018. [Online]. https://doi.org/10.5562/cca3344

Sažetak
Square-planar substitution reactions (chlorido for iodide, trans to methyl and hydrido as non-labile ligands) was kinetically investigated in chloroform solution in a series of platinum(II) trans-[PtRCl(L)2] complexes (R = Me: L = PPh3, 1; PPh2Fc, 2; P(NMe2)3, 3; AsPh3, 5; As(4-Me-Ph)3, 6; R = H: L = PPh3, 7) and cis-[PtMeCl(Ph2PFcPPh2)], 4. The reactions follow the normal associative mode of activation, but with equilibria present in all steps, with rate constants for the direct substitution pathway, k12, of (9.1 ± 1.0) × 10−4, 0, (1.389 ± 0.016)×10−2, (1.51 ± 0.15), (2 ± 4) × 10−3, (2.79 ± 0.04) × 10−2 and 0 mol−1 dm3 s−1 at 298 K for 1 to 7 respectively. The corresponding second order rate constants for the solvent assisted pathway, k13', were also determined. The activation parameters for the direct and solvent assisted pathways for 3 were determined as ΔH = 60.4 ± 1.4 and 53.7 ± 0.3 kJ mol−1, and ΔS = −78 ± 4 and −142 ± 1 J mol−1 K−1. A significant more than four orders-of-magnitude reactivity range was observed. Crystal structures of trans-[PtMeCl(PPh2Fc)2].2CHCl3.2H2O, trans-[PtMeCl{P(NMe2)3}2], cis-[PtMeCl(Ph2PFcPPh2)].2CHCl3 and trans-[PtHCl(PPh3)2].CH3OH are reported.

Creative Commons License This work is licensed under a Creative Commons Attribution 4.0 International License.

Ključne riječi
square-planar substitution; platinum{II}; methyl/ hydrido complexes; associative activation; kinetics; equilibria; crystallography

Hrčak ID: 203604

URI
https://hrcak.srce.hr/203604

Posjeta: 490 *