Coordination Chemistry and Asymmetric Homogeneous Catalysis
Manuel Alcarazo has moved to the University of Göttingen as Professor for Organic Chemistry in December 2015. Information on his current research is available here. This web page documents the activities of his group at the Max-Planck-Institut für Kohlenforschung (until 2015).
Research in our group is primarily directed toward the coordination chemistry of main group element in unusual oxidation states, the design of novel “frustrated Lewis pairs” and applications thereof to homogeneous catalysis and organic synthesis.
Dr. Manuel Alcarazo
- since 2015
- Professor for Organic Chemistry at Georg-August University Göttingen
- since 2008
- Independent Junior Group Leader at the Max-Planck-Institut für Kohlenforschung
- 2005-2008
- Postdoctoral research at the Max-Planck-Institut für Kohlenforschung (Prof. Dr. Alois Fürstner) on the “Design and applications of ylidic and bis-ylidic systems” and “Enantioselective protecting group-free total synthesis of ecklonialactone A and B”
- 2005
- PhD from the Instituto de Investigaciones Químicas (CSIC) (Dr. José M. Lassaletta) on the “Synthesis and structure of new NHC-ligands”
- 2002
- Master Degree from the University of Seville, Spain (Prof. Dr. Rosario Fernández) on the “Synthesis and applications of bis-hydrazones as ligands in asymmetric catalysis”
- 2000
- Chemistry Degree from the University of Seville, Spain
- 1978
- born in Alcalá de Guadaira, Spain
- 2013
- Young Scientist Award from the Academy of Sciences of Göttingen
- 2013
- ADUC Annual Prize for Habilitands 2012
- 2013
- Science Award of the Industrie-Club Duesseldorf and the North Rhine-Westphalian Academy of Sciences, Humanities and the Arts
- 2013-2017
- Lecturer's scholarship ("Dozentenstipendium") of the Chemical Industry Fund
- 2012
- Sponsorship Award of Dr. Otto Roehm Commemoration Foundation
- 2011
- European Research Council Starting Grant for his research “Activation of small molecules by organic frustrated Lewis pairs"
- 2011
- Sigma-Aldrich-RSEQ Prize for Outstanding Emerging Researcher
- 2010
- Thieme Journal Award 2010
- 2009
- Young Scientist Award from the Academy of Sciences of Seville, Spain
- 2007
- Best PhD Thesis in Chemistry, University of Seville, Spain
- 2005-2007
- Post-Doctoral Fellowship of the Spanish Ministry of Education and Science
- 2005
- Research Fellowship from the Spanish Council for Scientific Research (CSIC)
- 2001-2005
- PhD Scholarship from the Spanish Ministry of Education and Science (Short stays at Aarhus, Denmark (Prof. K. A. Jørgensen) and Oxford, United Kingdom (Prof. J. M. Brown))
- 2001
- Scholarship from the Spanish Agency of International Cooperation (Universidad Nacional Autónoma de México)
- 2000
- Graduation Prize from the University of Seville, Spain
- 2000
- Cooperation Scholarship with the Department of Organic Chemistry, University of Seville, Spain
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Total Synthesis (I), TU Dortmund, WS 2009/2010
Principles in Organometallic Chemistry, TU Dortmund, SS 2010
Stereoselective Synthesis (I), TU Dortmund, WS 2010/2011
Stereoselective Synthesis (II), TU Dortmund, SS 2011
Total Synthesis (I), TU Dortmund, WS 2011/2012
Stereoselective Synthesis, Heinrich-Heine University Düsseldorf, SS 2012 (please find the slides here)
- since 2014
- Member of the Editorial Advisory Board of "Organometallics"
- since 2009
- Member of Global Young Faculty
- since 2008
- Group leader at the Max-Planck-Institut für Kohlenforschung
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Organometallic Chemistry (II), TU Dortmund, WS 2013/2014
Organometallic Chemistry (I), TU Dortmund, SS 2013
Stereoselective Synthesis, Heinrich-Heine University Düsseldorf, SS 2012
Total Synthesis (I), TU Dortmund, WS 2011/2012
Stereoselective Synthesis (II), TU Dortmund, SS 2011
Stereoselective Synthesis (I), TU Dortmund, WS 2010/2011
Principles in Organometallic Chemistry, TU Dortmund, SS 2010
Total Synthesis (I), TU Dortmund, WS 2009/2010
Research Topics
- Cationic ligands: synthesis and applications of extreme π-acid catalysts
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Cationic ligands: synthesis and applications of extreme π-acid catalysts
The goal of this project is the synthesis of extreme π-acceptor phosphines through the introduction of positively charged homo- or heteroaromatic substituents directly attached to the phosphorus atom. By exploiting this property, new Au and Pt catalysts have been developed that display a dramatically enhanced capacity to activate π-systems.
Very recently, we reported the synthesis of the first ever isolated carbene-stabilized P1-centered trication [L3P]3+ (L = 2,3-dialkylaminocyclopropenium) 1 by reaction of the 1-chloro-2,3-(dimethylamino) cyclopropenium salt 2 and P(SiMe3)3 (Scheme 1). Despite the three positive charges on the groups directly attached to the P atom, this compound can still serve as a ligand for π-acidic metals such as Pt. Thus, when 1 is treated with K2PtCl4 in acetonitrile, the bench stable complex 3 is formed. More interestingly, charge decomposition analysis of the metal-ligand interaction in 3 gave the surprising result that the total L→M σ-donation (0.31 e) is lower than the L→M π-back donation (0.43 e) into the very low-lying LUMO of 1, which must hence be regarded as the main interaction in 3. This unconventional situation in which the P-ligand removes net electron density from the metal suggests that compound 1 increases the natural π-acidity of Pt(II) centers. It should thus accelerate known reactions, or even permit new ones, in which either the coordination of the substrate or the nucleophilic attack to the activated substrate are the rate-determining steps.
Accordingly, we chose for our studies on ligand effects a series of phosphanes such as PPh3, P(OPh)3, P(C6F5)3 and precatalyst 3 in combination with a silver salt. As expected, both P(OPh)3 and P(C6F5)3 performed better than PPh3 in terms of reactivity (Scheme 2).
In addition, our synthetic program has already benefitted from these novel tools and natural products such as Orchinol, Ochrolide, Bulbophyllantrin and Epimedoicarisoside A have been prepared using our Pt and Au catalysts for the key hydroarylation step (Scheme 3).
- Synthesis and applications of simultaneous σ- and π-donor ligands: C-M dative double bonds
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Synthesis and applications of simultaneous σ- and π-donor ligands: C-M dative double bonds
In this area, our research has been strongly inspired by the theoretical work of Frenking about the nature of carbodiphosphorane 1 (Scheme 1). His studies revealed that in compound 1 and analogues the central carbon atom retains its four valence electrons that are thus all available for coordination. In fact, carbodiphosphoranes are known to react with two Lewis acids such as AuCl affording diaurated derivatives. However, their ability to donate their four electrons to the same electrophile in a simultaneous σ- and π-donation had not been described.
In this regard, we envisaged that the use carbodiphosphoranes may provide sufficient stabilization to attenuate the reactivity and allow the isolation of dihydrido borenium cations [L→BH2]+ (L = carbodiphosphorane), a series of compounds that cannot be isolated when classical σ-donating ligands are employed.
Our strategy is already producing some positive results with other low valent cations. Up to now we have been able to synthesize compound 4 which already depicts a σ- and π-dative bond between the central carbon atom and the GeCl moiety. Reaction with dimethylamino pyridine affords adduct 5 where the π interaction is not existing anymore.
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Staff
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Dr. Abdellah, Ibrahim
Oct 12 – Sep 13 Post-doc
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Dr. Alcarazo, Manuel
Jul 05 – Nov 08 Post-doc; Dec 08 – Dec 15 Group Leader
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Dr. Alonso García, Isaac
Jul 14 – Jul 15 Post-doc
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Alvarez Méndez, Sergio Joaquin
Aug 13 – Oct 13 Visiting PhD Student
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Averesch, Kai
Jul 15 – Dec 15 PhD Student
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Dr. Carreras, Javier
Jan 11 – Feb 13 Post-doc
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Costa, Paolo
Dec 11 – Apr 12 PhD Student
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Deden, Tobias
Jan 13 – Aug 13 MSc Student
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Dr. Dube, Jonathan W.
Jun 14 – Dec 15 Post-doc
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García Barrado, Alejandro
Sep 13 – Dec 15 PhD Student
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Gimeno Cardells, Ana Maria
Jun 12 – Sep 12 Visiting PhD Student
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Gonzalez Fernández, Elisa
Apr 12 – Dez 15 PhD Student
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Gu, Lianghu
Sep 12 – Dec 15 PhD Student
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Dr. Gualco, Pauline
May 12 – Apr 13 Post-doc
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Dr. Haldón Hermoso, Estela
Oct 13 – June 15 Post-doc
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Dr. Iglesias Sigüenza, Francisco J.
Jul 11 - Jun 12 Post-doc
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Dr. Ines Tejedor, Blanca
Jan 10 – Dec 11 Post-doc; Jan 12 – Dec 12 Scientific Co-worker
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Dr. Khan, Shabana
Oct 11 – Dec 12 Scientific Co-worker
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Klein, Betina
Sep 09 – Jan 13 Trainee/Technical Staff
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Kozma, Ágnes
Oct 11 – Aug 15 PhD Student
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López Rodríguez, Maria del Rocío
Jun 14 – Sep 14 Visiting PhD Student
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Linowski, Pawel
Jul 12 – Jun 15 PhD Student
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Lutz, Sigrid
+49(0)208/306-2474
s_lutz((atsign))kofo.mpg.de
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Dr. Martín Gálvez, Francisca María
Feb 13 – Feb 14 post-doc
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Mehler, Gerlinde
Aug 70 – Feb 18 Technical Staff
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Nicasio Collazo, Juan Antonio
May 12 – Apr 13 Visiting PhD Student
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Nicholls, Leo David Mwenya
Apr 14 – Dec 15 PhD Student
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Pérez Aguilar, María del Carmen
May – Jul 14 Visiting PhD Student
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Dr. Palomas Dona, David
Mar 10 – Feb 12 Post-doc
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Dr. Peña Gonzalez, Javier
Jul 14 – Dec 15 Post-doc
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Petuškova, Jekaterina
Apr 09 – Mar 12 PhD Student
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Prades Ferrer, Amparo
Sep 11 – Nov 11 Visiting PhD Student
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Dr. Ramachandran, Azhakar
May 13 – May 14 Post-doc
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Schauenburg, Dominik
Jan 13 – Mar 13 BSc Student
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Steinberg, Sebastian
Jan 12 – Mar 15 PhD Student
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Dr. Talavera Urquijo, Garazi
Jul 13 – Dec 15 Post-doc
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Tinnermann, Hendrik
Nov 12 – Dec 15 PhD Student
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Truckenbrodt, Jens
Jul 11 – Jan 12 Permanent Staff
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Waldecker, Bernd
Jul 15 – Dec 15 PhD Student
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Dr. Zanardi, Alessandro
Jan 13 – Apr 13 Post-doc; May 13 – Mar 14 Scientific Co-worker
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Dr. Zhang, Yin
Oct 15 – Dec 15 Post-doc
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Zielinski, Adam
Oct 15 – Dec 15 Post-doc
