Hydrolysis of chlorido complexes of d8 metals: Old models, new
facts

J 2019

Hydrolysis of chlorido complexes of d8 metals: Old models, new facts

KOZELKA, Jiří

Základní údaje

Originální název

Hydrolysis of chlorido complexes of d8 metals: Old models, new facts

Autoři

KOZELKA, Jiří (203 Česká republika, garant, domácí)

Vydání

Inorganica Chimica Acta, Lausanne, Elsevier, 2019, 0020-1693

Další údaje

Jazyk

angličtina

Typ výsledku

Článek v odborném periodiku

Obor

10402 Inorganic and nuclear chemistry

Stát vydavatele

Nizozemské království

Utajení

není předmětem státního či obchodního tajemství

Odkazy

URL

Impakt faktor

Impact factor: 2.304

Kód RIV

RIV/00216224:14310/19:00110712

Organizační jednotka

Přírodovědecká fakulta

DOI

http://dx.doi.org/10.1016/j.ica.2019.05.045

UT WoS

000481728800015

EID Scopus

2-s2.0-85067807309

Klíčová slova anglicky

Square-planar substitution; Hydrolysis; Aquation kinetics; Charge-separation effect; Cisplatin; d8 complexes

Štítky

rivok

Příznaky

Mezinárodní význam, Recenzováno

Změněno: 24. 3. 2020 17:24, Mgr. Marie Novosadová Šípková, DiS.

Anotace

V originále

The discovery of the antitumor activity of cisplatin in 1969 has accelerated research in platinum chemistry. In particular, cisplatin hydrolysis, the rate-determining process activating the drug for reaction with DNA, was extensively studied and discussions of the mechanism of square-planar substitutions were rekindled. One intriguing aspect of cisplatin hydrolysis is the fact that the rates of the two aquation steps are almost identical, in spite of the charge-separation effect which would be expected to slow down the second step. This result is analyzed here in the context of the more general observation made by Martin et al. that aquation of chloridoammine complexes of Pt(II) proceeds at similar rates, independently of complex charge. Ancient hypotheses put forward to explain this observation are confronted with recent data. The discussion is extended to aquation of chlorido-am(m)ine complexes of Pd(II) and Au(III), and to chloride substitutions by thiourea and pyridine. It is shown that the charge independence is not limited to chloride substitution by water. This new correlation of published data invalidates our recent hypothesis according to which non-conventional hydrogen bonding from the attacking water molecule to the Pt(II) center as acceptor counterbalances the charge separation effect. Recent data also show that the frequently used kinetic model for square-planar substitutions featuring a metastable five-coordinate intermediate does not apply to complexes involving only simple o-donating ligands such as amines, water, or chloride. By inference, the Martin-Basolo model, explaining the charge-independence of aquation rate constants with the mutual compensation between charge separation and charge neutralization in the transition state, remains the only model compatible with available data.

Citovat

KOZELKA, Jiří. Hydrolysis of chlorido complexes of d8 metals: Old models, new facts. Inorganica Chimica Acta. Lausanne: Elsevier, 2019, roč. 495, SEP 1 2019, s. 1-8. ISSN 0020-1693. Dostupné z: https://dx.doi.org/10.1016/j.ica.2019.05.045.

@article{1558677,
   author = {Kozelka, Jiří},
   article_location = {Lausanne},
   article_number = {SEP 1 2019},
   doi = {http://dx.doi.org/10.1016/j.ica.2019.05.045},
   keywords = {Square-planar substitution; Hydrolysis; Aquation kinetics; Charge-separation effect; Cisplatin; d8 complexes},
   language = {eng},
   issn = {0020-1693},
   journal = {Inorganica Chimica Acta},
   title = {Hydrolysis of chlorido complexes of d8 metals: Old models, new facts},
   url = {https://www.sciencedirect.com/science/article/pii/S0020169319304918},
   volume = {495},
   year = {2019}
}

TY  - JOUR
ID  - 1558677
AU  - Kozelka, Jiří
PY  - 2019
TI  - Hydrolysis of chlorido complexes of d8 metals: Old models, new facts
JF  - Inorganica Chimica Acta
VL  - 495
IS  - SEP 1 2019
SP  - 1-8
EP  - 1-8
PB  - Elsevier
SN  - 00201693
KW  - Square-planar substitution
KW  - Hydrolysis
KW  - Aquation kinetics
KW  - Charge-separation effect
KW  - Cisplatin
KW  - d8 complexes
UR  - https://www.sciencedirect.com/science/article/pii/S0020169319304918
L2  - https://www.sciencedirect.com/science/article/pii/S0020169319304918
N2  - The discovery of the antitumor activity of cisplatin in 1969 has accelerated research in platinum chemistry. In particular, cisplatin hydrolysis, the rate-determining process activating the drug for reaction with DNA, was extensively studied and discussions of the mechanism of square-planar substitutions were rekindled. One intriguing aspect of cisplatin hydrolysis is the fact that the rates of the two aquation steps are almost identical, in spite of the charge-separation effect which would be expected to slow down the second step. This result is analyzed here in the context of the more general observation made by Martin et al. that aquation of chloridoammine complexes of Pt(II) proceeds at similar rates, independently of complex charge. Ancient hypotheses put forward to explain this observation are confronted with recent data. The discussion is extended to aquation of chlorido-am(m)ine complexes of Pd(II) and Au(III), and to chloride substitutions by thiourea and pyridine. It is shown that the charge independence is not limited to chloride substitution by water. This new correlation of published data invalidates our recent hypothesis according to which non-conventional hydrogen bonding from the attacking water molecule to the Pt(II) center as acceptor counterbalances the charge separation effect. Recent data also show that the frequently used kinetic model for square-planar substitutions featuring a metastable five-coordinate intermediate does not apply to complexes involving only simple o-donating ligands such as amines, water, or chloride. By inference, the Martin-Basolo model, explaining the charge-independence of aquation rate constants with the mutual compensation between charge separation and charge neutralization in the transition state, remains the only model compatible with available data.
ER  -

KOZELKA, Jiří. Hydrolysis of chlorido complexes of d8 metals: Old models, new facts. \textit{Inorganica Chimica Acta}. Lausanne: Elsevier, 2019, roč.~495, SEP 1 2019, s.~1-8. ISSN~0020-1693. Dostupné z: https://dx.doi.org/10.1016/j.ica.2019.05.045.

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