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Coordination Chemistry and Asymmetric Homogeneous Catalysis

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.

Manuel Alcarazo

Dr. Manuel Alcarazo

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

 

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
 

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

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

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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  • Dr. Ibrahim Abdellah

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