Kinetic studies on substitution reactions of Delepine's triangular mixed-valence iridium(III, IV, IV) complex triaqua(.mu.3-nitrido)(hexa-.mu.-sulfato)triiridate(4-)

1986 ◽  
Vol 25 (18) ◽  
pp. 3144-3148 ◽  
Author(s):  
Elaine F. Hills ◽  
David T. Richens ◽  
A. Geoffrey Sykes
Keyword(s):  
Mixed Valence ◽  
Kinetic Studies ◽  
Substitution Reactions

Exploring the acid-catalyzed substitution mechanism of [Fe4S4Cl4]2−

2016 ◽  
Vol 45 (1) ◽  
pp. 307-314 ◽  
Author(s):  
Thaer M. M. Al-Rammahi ◽  
Richard A. Henderson
Keyword(s):  
Bond Cleavage ◽  
Kinetic Studies ◽  
Substitution Reactions ◽  
Substitution Mechanism ◽  
Acid Catalyzed

Kinetic studies focussing on either the protonation or substitution step of the acid catalyzed substitution reactions of [Fe4S4Cl4]2− support a mechanism involving concomitant cluster protonation and Fe–(μ3-SH) bond cleavage.

Kinetic Studies on the Reactions of [(TLtBu)PtCl]+ and [Pt(tpdm)Cl]+ Complexes with Some Thiols and Thioethers

2013 ◽  
Vol 66 (5) ◽  
pp. 534 ◽  
Author(s):  
Enisa Selimović ◽  
Biljana Petrović ◽  
Dragan Čcanović ◽  
Živadin D. Bugarčić ◽  
Jovana Bogojeski
Keyword(s):  
Variable Temperature ◽  
Kinetic Studies ◽  
Substitution Reactions ◽  
Tert Butyl ◽  
Naclo4 Solution ◽  
Entropy Of Activation ◽  
Methyl Pyridine

Substitution reactions of the complexes [(TLtBu)PtCl]+ and [Pt(tpdm)Cl]+, where TLtBu = 2,6-bis[(1,3-di-tert-butylimidazolin-2-imino)methyl]pyridine and tpdm = terpyridinedimethane, with nucleophiles: S-methyl-L-cysteine (S-Met-L-Cys), L-cysteine (L-Cys), glutathione (GSH) and L-methionine (L-Met) were studied in aqueous 0.1 M NaClO4 solution in the presence of 10 mM NaCl using variable-temperature UV-vis spectrophotometry. The higher reactivity of the complex with the tpdm ligand could be attributed to the influence of the bulkiness of the tert-butyl-groups from the [(TLtBu)PtCl]+ complex. The order of reactivity of the studied ligands is: S-Met-L-Cys > L-Met > GSH > L-Cys. The thioethers (S-Met-L-Cys and L-Met) are more reactive than the thiols (GSH and L-Cys). This order of reactivity is in relation with their electron properties and structures. The negative values reported for the entropy of activation confirmed the associative mode.

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