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Aquation
About: Aquation is a research topic. Over the lifetime, 1443 publications have been published within this topic receiving 17507 citations.
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TL;DR: The rate-determining dissociation of the outgoing group (Cl− or HgCl+) takes place via either a square-pyramidal or a trigonal-bipyramidal intermediate, depending on whether the activation entropy is negative or positive as discussed by the authors.
Abstract: Salts of one isomeric form of the chloro-n-butylamine-, chloro-iso-butyl-amine- and chloro-sec-butylamine-bis(ethylenediamine)cobalt(III) cations have been prepared and characterised to have a cis-configuration (IR and VIS spectroscopy). Rate constants for their spontaneous aquation, mercury(II)-induced aquation and base hydrolysis have been determined and the activation parameters calculated. The results are compared with data obtained for the n-propylamine complex with a view to investigate the effects of methyl (α, β, γ) substituents on reactivities.
The rate-determining dissociation of the outgoing group (Cl− or HgCl+) takes place via either a square-pyramidal or a trigonal-bipyramidal intermediate, depending on whether the activation entropy is negative or positive.
Salze einer isomeren Form des Chloro-n-butylamin-, Chloro-iso-butylamin- und Chloro-sec-butylamin-bis(atylendiamin)-kobalt(III)-Kations wurden dargestellt und spektroskopisch als Komplexe mit cis-Konfiguration charakterisiert. Die Geschwindigkeitskonstanten des spontanen bzw. durch HgII induzierten Ligandenaustausches mit H2O und des hydrolytischen OH-Eintausches wurden bestimmt und die Aktivierungsparameter berechnet. Die Ergebnisse werden mit den an den n-Propylaminkomplexen erhaltenen verglichen, besonders in Hinsicht auf den Einflus der (α, β, γ) Methylgruppen auf die Reaktivitaten. Die geschwindigkeitsbestimmende Abdissoziation von Cl-oder HgCl+ verlauft entweder uber einen quadratisch-pyramidalen oder einen trigonal-bi-pyramidalen Zwischenzustand, je nachdem, ob die Aktivierungsentropie negativ oder positiv ist.
6 citations
6 citations
6 citations
TL;DR: The rate of aquation of tris(malonato)cobaltate (III) anion was studied in 0·10-0·30 M HClO 4 (μ = 0· 10−1·0 M NaClO4) as discussed by the authors.
6 citations
TL;DR: The results demonstrate that guanine is superior to other biomolecules in terms of coordinating with the RuII aqua adduct, which is in reasonable agreement with experimental observations.
Abstract: The piano-stool RuII arene complex [(η6-benz)Ru(bpm)(py)]2+ (benz = benzene, bpm = 2,2′-bipyrimidine, and py = pyridine), which is conventionally nonlabile (on a timescale and under conditions relevant for biological reactivity), can be activated by visible light to selectively photodissociate the monodentate ligand (py). In the present study, the aquation and binding of the photocontrolled ruthenium(II) arene complex [(η6-benz)Ru(bpm)(py)]2+ to various biomolecules are studied by density functional theory (DFT) and time-dependent DFT (TDDFT). Potential energy curves (PECs) calculated for the Ru–N (py) bonds in [(η6-benz)Ru(bpm)(py)]2+ in the singlet and triplet state give useful insights into the photodissociation mechanism of py. The binding energies of the various biomolecules are calculated, which allows the order of binding affinities among the considered nuleic-acid- or protein-binding sites to be discerned. The kinetics for the replacement of water in the aqua complex with biomolecules is also considered, and the results demonstrate that guanine is superior to other biomolecules in terms of coordinating with the RuII aqua adduct, which is in reasonable agreement with experimental observations.
6 citations