NDLI: The role of hydroxo-bridged dinuclear species and the influence of “innocent” buffers in the reactivity of $cis-[Co^{III}(cyclen)(H_{2}O)_{2}]^{3+}$ and $[Co^{III}(tren)(H_{2}O)_{2}]^{3+}$ complexes with biologically relevant ligands at physiological pH

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The role of hydroxo-bridged dinuclear species and the influence of “innocent” buffers in the reactivity of $cis-[Co^{III}(cyclen)(H_{2}O)_{2}]^{3+}$ and $[Co^{III}(tren)(H_{2}O)_{2}]^{3+}$ complexes with biologically relevant ligands at physiological pH

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The role of hydroxo-bridged dinuclear species and the influence of “innocent” buffers in the reactivity of $cis-[Co^{III}(cyclen)(H_{2}O)_{2}]^{3+}$ and $[Co^{III}(tren)(H_{2}O)_{2}]^{3+}$ complexes with biologically relevant ligands at physiological pH

Content Provider	World Health Organization (WHO)-Global Index Medicus
Author	Martínez, Manuel Vázquez, Marta Basallote, Manuel G.
Description	Author Affiliation: Basallote MG ( Departamento de Ciencia de los Materiales e Ingeniería Metalúrgica y Química Inorgánica, Universidad de Cádiz, Apartado 40, E-11510 Puerto Real, Cádiz, Spain.)
Abstract	In view of the relevance of the reactivity of inert tetraamine $Co^{III}$ complexes having two substitutionally active cis positions capable of interact with biologically relevant ligands, the study of the reaction of $cis-[Co(cyclen)(H_{2}O)_{2}]^{3+}$ and $[Co(tren)(H_{2}O)_{2}]^{3+}$ with chlorides, inorganic phosphate and 5′-CMP (5′-cytidinemonophosphate) has been pursued at physiological pH. The results indicate that, in addition to the actuation of the expected labilising conjugate-base mechanism, the formation of mono and inert bis hydroxo-bridged species is relevant for understanding their speciation and reactivity. The reactivity pattern observed also indicates the key role played by the “innocent” buffers frequently used in most in vitro studies, which can make the results unreliable in many cases. The differences between the reactivity of inorganic and biologically relevant phosphates has also been found to be remarkable, with outer-sphere hydrogen bonding interactions being a dominant factor for the process. While for the inorganic phosphate substitution process the formation of $μ–η^{2}-OPO_{2}O$ represents the termination of the reactivity monitored, for 5′-CMP only the formation of $η^{1}-OPO_{3}$ species is observed, which evolve with time to the final dead-end bis hydroxo-bridged complexes. The promoted hydrolysis of the 5′-CMP phosphate has not been observed in any of the processes studied.
ISSN	14779226
Issue Number	28
Volume Number	43
e-ISSN	13645447
Journal	Dalton Trans.
Language	English
Publisher	Royal Society of Chemistry
Publisher Date	2014-07-28
Publisher Place	Great Britain (UK)
Access Restriction	Subscribed
Subject Keyword	Bridged Compounds Chemistry Cobalt Coordination Complexes Ethylenediamines Heterocyclic Compounds Buffers Hydrogen-Ion Concentration Ligands Molecular Conformation Journal Article Research Support, Non-U.S. Gov't
Content Type	Text
Resource Type	Article
Subject	Inorganic Chemistry

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