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Izvorni znanstveni članak
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 | citiraj | |
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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 |
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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.
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
Moj profil
Srce