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6MECANISMES

Departament de Química Inorgànica                        Català
Facultat de Química                                                   Castellano
Universitat de Barcelona                                          English
Martí i Franquès 1-11
E-08028 Barcelona

GROUP

INTRODUCTION

RESEARCH FIELDS

POSTGRADUATE STUDIES

COLLABORATIONS

PUBLICATIONS

December 2006

GROUP

The Reaction Mechanisms in Inorganic Chemistry group is a small group directed by the full professor Dr. Manuel Martínez López.

Presently, Mr. Fernando Bozoglian Tatlian and Carlos Rodríguez del Rio are also members of the group as Ph.D. srudents.

The group has its own equipment for the measurement of reaction kinetics, including two stopped-flow instruments, two standard spectrophotometer with five- and twelve-cell holders, a standard diode-array spectrophotometer with seven-cell holder, a diode-array spectrophotometer of 0.8 ms, and a system for the pressurization of liquids up to 2500 atm which allows the measurement of activation volumes.

Furthermore, all the instrumentation belonging to the Department de Química Inorgànica, the Facultat de Química and the Serveis Científico-Tècnics from the Universitat de Barcelona is commonly used by the group.

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INTRODUCTION

There is great interest in the ability to adjust and tune reaction mechanisms through systematic modification, not only of the steric and electronic environment of the reacting species, but also of the reaction conditions.

In addition to the academic interest per se of these studies, it is obvious than a better knowledge of the mechanism through which a reaction occurs will lead to an optimization of the processes regarding selectivity, economy, temperature and pressure conditions, and the presence of any possible catalyzing species.

The group's project intends to increase the mechanistic information available on previously known reactions, while introducing very systematic modifications to the electronic and steric properties of the reacting species. The goal is to establish up to which point and, in which cases, it is possible to fine tune the reactivity.

RESEARCH FIELDS

The Mecanismes de Reacció en Química Inorgànica group has received financial support for the development of its research on numerous occasions. This financial support has been granted not only for the development of research projects, but also for the increase of the group's research infrastructure.

The group's global line of research is based on the modulation of the reactivity of inorganic compounds though the fine tuning of the reaction mechanism. The following lines have allowed the group to advance towards its objective:

Kinetico-mechanistic studies on activation processes of C-X bonds by Pt(II) and Pd(II) complexes.

Study of steric and electronic effects on the intimate substitution mechanism on Co(III) and Cr(III) complexes, through variations of the activation volume.

Study of the mechanism of redox and formation processes on Fe/Co mixed-valence compounds with macrocyclic ligands and cyanide bridges.

Study of the steric and electronic influence on the substitution processes of Pt(IV) organometallic compounds.

Study of the substitution mechanism on complexes of formula [CoN₄L₂] with biologically relevant, nucleobase-derived ligands.

At this time, all of the above lines are being worked on intensively. Some of the subjects are specially indicated for the incorporation of new members in the group, which would result in an enhancement of the lines.

POSTGRADUATE STUDIES

Thus far dissertations of three Ph.D. thesis have been defended by members of the group (Gabriel González, Mari-Ángel Pitarque, Carlos Gallego Rubio and Julio Esteban) obtaining the maximum possible qualification. Presently, Mr. Fernando Bozoglian and Mr. Carlos Rodríguez are is doing their Ph.D. with very good results. Mr. Fernando Bozoglianis also at the moment finishing his PhD..

The group has also had postgraduate predoctoral students, whose contributions have increased the level of the research. All of these students (Ángel Sánchez, Gabriel González, Jordi Llorca, Mari-Ángel Pitarque, Esther de Pablo, Elisa Rodríguez, Júlio Esteban, Carlos Gallego) have accomplished work of a quality to merit publication in international journals.

Now the group offers Màster en Química Experimental on the following subjects:

Electrocromic products. Redox study of mixed-valence compounds with formula [LCo^III NC Fe^II(CN)₅]^- .

Synthesis and reactivity of cis-[Co(ciclen)Cl₂]Cl. Applications to bioinorganic models.

Study of the mechanims operating in substitution and C-X bond activation reactions on palladium and platinum organometallic compounds.

COLLABORATIONS

Owing to the small number of members of the group, a number of local, national and international collaborations have been established in order to increase scientific output.

LOCAL Dr. Margarita Crespo Vicente, Dr. Montserrat Gómez Simón, Dr. Jaume Granell Sanvicente, Dr. Virtudes Moreno Martínez

NATIONAL Dr. Manuel Garcia Basallote (Universidad de Cádiz), Dr. Pascual Lahuerta Peña (Universitat de València), Dr. Sixte Safont (Universitat de Castelló).

INTERNATIONAL Dr. Paul Bernhardt (University of Queensland, Australia), Dr. Geoffrey Lawrance (University of Newcastle, Australia), Dra. Beatriz Sienra (Universidad de la República, Uruguay), Dr. Rudi van Eldik (Univesität Erlangen, Alemanya), Dr. André Merbach (Université de Lausanne, Switzerland).

PUBLICATIONS

The following publications are a sample of the research work carried out by the group:

Arnau, C.; Martínez, M.; Sánchez, A.; Ferrer, M. Journal of the Chemical Society, Dalton Transactions 1839(1985)

Ferrer, M.; González, G.; Martínez, M. Journal of the Chemical Society, Dalton Transactions 2597(1990)

Ferrer, M.; Martínez, M.; Pitarque, M.A. Journal of the Chemical Society, Dalton Transactions 1629(1990)

Ferrer, M.; Llorca, J.; Martínez, M. Journal of the Chemical Society, Dalton Transactions 229(1992)

González, G.; Martínez, M. Inorganica Chimica Acta 230, 67(1995)

Martínez, M.; González, G.; Rodríguez, E. Journal of the Chemical Society, Dalton Transactions 891(1995)

Martínez, M.; Muller, G.; Panyella, D.; Rocamora, M.; Sales, J.; Solans, X.; Font-Bardía, M. Organometallics 14, 5552(1995)

Martínez, M.; Pitarque, M.A. Journal of the Chemical Society, Dalton Transactions 4107(1995)

Estevan, F.; González, G.; Lahuerta, P.; Martínez, M.; Peris, E.; van Eldik, R. Journal of the Chemical Society, Dalton Transactions 1045(1996)

Martínez, M.; Pitarque, M.A.; van Eldik, R. Journal of the Chemical Society, Dalton Transactions 2665(1996)

Martínez, M.; Pitarque, M.A.; van Eldik, R. Inorganica Chimica Acta 256, 51(1997)Crespo, M.; Martínez, M.; de Pablo, E. Journal of the Chemical Society, Dalton Transactions 1321(1997)

Gómez, M.; Granell, J.; Martínez, M. Organometallics 16, 2539(1997)

Gómez, M.; Granell, J.; Martínez, M. Journal of the Chemical Society, Dalton Transactions 37(1998)

Alarcón, C.J.; Estevan, F.; Lahuerta, P.; Ubeda, M.A.; González, G.; Martínez, M. Inorganica Chimica Acta 278, 61(1998)

Basallote, M.G.; Durán, J.; Fernández-Trujillo, M.J.; González, G.; Máñez, M.A.; Martínez, M. Inorganic Chemistry 37, 1623(1998)

Bernhardt, P.V.; Martínez, M. Inorganic Chemistry 38, 424(1999)

de Barrios, N.; González, G.; Grandas, A.; Martinez, M.; Moreno, V. Inorganic Reaction Mechanisms 1, 205(1999)

Basallote, M.G.; Durán, J.; Fernández-Trujillo, M.J.; González, G.; Máñez, M.A.; Martínez, M. Journal of the Chemical Society, Dalton Transactions 3379(1999)

Benzo, F.; Bernhardt, P.V.; González, G.; Martínez, M.; Sienra, B. Journal of the Chemical Society, Dalton Transactions 3973(1999)

Baran, Y.; Lawrance, G.A.; Martínez, M.; Wilkes, E.N. Inorganic Reaction Mechanisms 1, 315(2000)

González, G.; Martínez, M.; Rodríguez, E. European Journal of Inorganic Chemistry 333(2000)

Martínez, M.; Gómez, M.; Granell, J. European Journal of Inorganic Chemistry 217(2000)

Bernhardt, P.V.; Gallego, C.; Martinez, M. Organometallics19, 4862(2000)

Bernhardt, P.V.; Macpherson, B.P.Martinez, M. Inorganic Chemistry 39, 5203(2000)

Benzo, F.; González, G.; Martinez, M.; Sienra, B. Inorganic Reaction Mechanisms 3, 25(2001)

de Juan, A.; Maeder, M.; Martinez, M.; Tauler, R. Analytica Chimica Acta 442, 337(2001)

Bozoglian, F.; Gonzalez, G.; Martinez, M.; Queirolo, M.; Sienra, B. Inorganica Chimica Acta 318, 191(2001)

Gómez, M.; Granell, J.; Martinez, M. Inorganic Chemistry Communications5, 67(2002)

Bernhardt, P.V.; Gallego, C.; Martinez, M., Parella, T. Inorganic Chemistry 41, 1747(2002)

Bernhardt, P.V.; McPherson, B; Martinez, M. Journal of the Chemical Society, Dalton Transactions 1435(2002)

Font-Bardía, M.; Gallego, C.; Martinez, M.; Solans, X. Organometallics 21, 3305(2002)

Font-Bardía, M.; Gallego, C.; González, G.; Martínez, M.; Merbach, A. E.; Solans, X. Dalton Transactions 1106(2003)

Esteban, J.; Font−Bardía, M.; Gallego, C.; González, G.; Martinez, M.; Solans, X. Inorganica Chimica Acta 351, 269(2003)

Bernhardt, P. V.; Bozoglian, F.; Macpherson, B. P.; Martínez, M.; González, G.; Sienra, B. European Journal of Inorganic Chemistry 2512(2003)

Crespo, M.; Font-Bardía, M.; Granell, J.; Martínez. M.; Solans, X. Dalton Transactions 3763(2003)

Gallego, C.; González, G.; Martínez, M.; Merbach, A.E. Organometallics 23 2434(2004)

Bernhardt, P. V.; Bozoglian, F.; Macpherson, B. P.; Martínez, M.; González, G.; Sienra, B. Dalton Transactions 2582(2004)

Sala, X.; Romero, S.; Rodríguez, M: Llobet, A.; González, G.; Martínez, M.; Benet-Buchholz, J. Inorganic Chemistry 43 5403(2004)

Bernhardt, P. V.; Bozoglian, F.; Macpherson, B. P.; Martínez, M.; Merbach, A.E.; González, G.; Sienra, B. Inorganic Chemistry 43 7187(2004)

Favier, I.; Gómez, M.; Granell, J.; Martínez. M.; Solans, X.; Font-Bardía, M. Dalton Transactions 123(2005)

Bernhardt, P. V.; Bozoglian, F.; Macpherson, B. P.; Martínez, M. Coordination Chemistry Reviews 249 1902(2005)

Bernhardt, P. V.; Bozoglian, F.; González, G.; Martínez, M.; Macpherson, B. P.; Sienra, B. Inorganic Chemistry 45 74(2006)

Pérez-Tejada, P.; López-Pérez, G.; Prado-Gotor, R.; Sánchez, F.; González-Arjona. D.; López-López, M.; Bozoglián, F.; González, G.; Martínez. M. Inorganica Chimica Acta 359 149(2006)

Aullón, G.; Bernhardt, P.V.; Bozoglián, F.; Font-Bardía, M.; Macpherson, B.P.; Martínez, M.; Rodríguez, C.; Solans, X., Inorganic Chemistry 45 8551(2006)

Esteban, J.; Hirva, P.; Lahuerta, P.; Martínez, M., Inorganic Chemistry 45 8776(2006)

Gómez, K.; González, G.; Martínez, M.; Mendoza, C.; Sienra, B., Polyhedron 25 3509(2006)