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D.G.H. (Dennis) Hetterscheid

dr. Dennis G. H. Hetterscheid

Worked on:

The main research theme in my career is to understand and mimic bioinorganic multi-electron processes such as H+, CO2, N2 and O2 reduction and H2O oxidation, and to apply these chemical transformations in electrochemical and photochemical “devices” for solar energy to fuel utilization. During my PhD I have worked on redox reactions at organometallic rhodium and iridium complexes  and I have carried out a PostDoc, concerning catalytic reduction of N2 by sequential addition of protons and electrons. At the University of Amsterdam iridium based water oxidation catalysts were developed funded by an independent VENI research grant. These iridium catalysts proved to be very efficient both in solution as well as upon spontaneous absorption on electrodes allowing for rapid electrochemical production of O2 and H2 (in combination with a platinum H+ reduction catalyst). In combination with various photosensitizers of appropriate redox strength, water oxidation was also demonstrated in a fully light driven approach. Currently, progress is being made to immobilize these catalyst on (semi)conducting surfaces and implementation of these water oxidation catalysts in prototype solar to fuel conversion devices. Although the VENI program is still running and several leads are still being explored, the research has already led to one patent and 4 papers (Angew. Chem. Int. Ed. 2009, 2012, Chem. Commun 2010, Organometallics 2010). Since iridium is a relatively expensive material focus is currently being shifted to the more abundant first row transition metals.

1.       Semisynthesis of 7-deoxypaclitaxel derivatives devoid of an oxetane D-ring, starting from taxine B, Beusker PH, Veldhuis H, Brinkhorst J, Hetterscheid DGH, Feichter N, Bugaut A, Scheeren HW, Eur. J. Org. Chem2003, 689.

2.       Disproportionation of Rh-II(cod) to Rh-I(cod) and Rh-III(cycloocta-2,5-dien-1-yl): Hydrogen atom transfer vs electron and proton transfer, Hetterscheid DGH , de Bruin B, Smits JMM, Gal AW, Organometallics 2003, 22, 3022.

3.       The electronic structure of (diiminopyridine)cobalt(I) complexes, Knijnenburg Q, Hetterscheid D, Kooistra TM, Budzelaar PHM, Eur. J. Inorg. Chem. 2004, 1204.

4.       Chemical ligand non-innocence in pyridine diimine Rh complexes, Kooistra TM, Hetterscheid DGH, Schwartz E, Knijnenburg Q, Budzelaar PHM, Gal AW, Inorg. Chim. Acta 2004, 357, 2945.

5.       Chloride-triggered disproportionation of a mononuclear Rh-II(nbd) species to Rh-I(nbd) and Rh-III(eta(1)-norbornenyl) complexes: Possibilities for Wacker type mono-oxygenation of norbornadiene to norbornenone, Hetterscheid DGH, Smits JMM, de Bruin B, Organometallics 2004, 23, 4236.

6.       Ir-II(ethene): Metal or carbon radical? Hetterscheid DGH, Kaiser J, Reijerse E, Peters TPJ, Thewissen S, Blok ANJ, Smits JMM, de Gelder R, de Bruin B, J. Am. Chem. Soc. 2005, 127, 1895.

7.       Ir-II(ethene): Metal or carbon radical? Part II: Oxygenation via iridium or direct oxygenation at ethene? Hetterscheid DGH, Bens M, de Bruin B, Dalton Trans. 2005, 979.

8.       Olefin hydrogenation using diimine pyridine complexes of Co and Rh, Knijnenburg Q, Horton AD, van der Heijden H, Kooistra TM, Hetterscheid DGH, Smits JMM, de Bruin B, Budzelaar PHM, Gal AW, J. Mol. Cat. A. Chem. 2005, 232, 151.

9.       Open-shell rhodium and iridium species in (catalytic) oxygenation reactions, Hetterscheid DGH, De Bruin B, J. Mol. Cat. A. Chem. 2006, 251, 291.

10.    Rhodium-mediated stereoselective polymerization of "carbenes", Hetterscheid DGH, Hendriksen C, Dzik, WI, Smits JMM, Van Eck, ERH, Rowan AE, Busico V, Vacatello M, Castelli VV, Segre A, Jellema E, Bloemberg TG, De Bruin B, J. Am. Chem. Soc. 2006, 128, 9746.

11.    Paramagnetic (alkene)Rh and (alkene)Ir complexes: Metal or ligand radicals? De Bruin B, Hetterscheid DGH, Eur. J. Inorg. Chem. 2007, 211.

12.    Hydrogen-atom transfer in open-shell organometallic chemistry: The reactivity of Rh-II(cod) and Ir-II(cod) radicals, Hetterscheid DGH, Klop M, Kicken RJNAM, Smits JMM, Reijerse EJ, De Bruin B, Chem. Eur. J. 2007, 3386.

13.    The organometallic chemistry of Rh-, Ir-, Pd-, Pt-based radicals: higher valent species, De Bruin B, Hetterscheid DGH, Koekkoek, AJJ, Grutzmacher H, Prog. Inorg. Chem. 2007, 55, 247.

14.    Deprotonation induced ligand-to-metal electron transfer: Synthesis of a mixed-valence Rh(-I,I) dinuclear compound and its reaction with dioxygen, Tejel C, Ciriano MA, Del Rio MP, Van den Bruele FJ, Hetterscheid DGH, Spithas NTI, De Bruin B, J. Am. Chem. Soc. 2008, 130, 5844.

15.    Ligand oxidation of a deprotonated bis(picolyl)amine Ir-I(cod) complex, Tejel C, Ciriano MA, Del Rio, MP, Hetterscheid DGH, Spithas NTI, Smits JMM, De Bruin B, Chem. Eur. J. 2008, 10932.

16.    Molybdenum triamidoamine systems. Reactions involving dihydrogen relevant to catalytic reduction of dinitrogen, Hetterscheid DGH, Hanna BS, Schrock RR, Inorg. Chem. 2009, 8569.

17.    S: Water splitting by cooperative catalysis, Hetterscheid DGH, Van der Vlugt, JI, De Bruin B, Reek JNH, Angew. Chem. Int. Ed. 2009, 48, 8178.

18.    Ligand-centred reactivity of bis(picolyl)amine iridium: Sequential deprotonation, oxidation and oxygenation of a “non-innocent” ligand, Tejel C, Del Rio MP, Ciriano MA, Reijerse EJ, Hartl F, Zalis S, Hetterscheid DGH, Spithas NTI, De Bruin B, Chem. Eur. J. 2009, 15, 11878.

19.    Formation of {{HIPTN3N]Mo(III)H}(-) by heterolytic cleavage of H2 as established by EPR and ENDOR spectroscopy, Kinney RA, Hetterscheid DGH, Hanna BS, Schrock RR, Hoffman BM, Inorg. Chem. 2010, 49, 704.

20.    S: Me2-NHC based robust Ir catalyst for efficient water oxidation, Hetterscheid DGH, Reek JNH, Chem. Commun. 2011, 47, 2712.

21.    S: Binuclear [(cod)(Cl)Ir(bpi)Ir(cod)]+ for catalytic water oxidation, W. I. Dzik, S. E. Calvo, J. N. H. Reek, M. Lutz, M. A. Ciriano, C. Tejel, D. G. H. Hetterscheid, B. De Bruin, Organometallics 2011, 30, 372.

22.    Cooperative double deprotonation of bis(2-picolyl)amine leading to unexpected bimetallic mixed valence (M-I, MI) rhodium and iridium complexes, C. Tejel, M. P. Del Rio, L. Asensio, F. J. van den Bruele, M. A. Ciriano, N. Tsichlis i Spithas, D. G. H. Hetterscheid, B. De Bruin, Inorg. Chem. 2011, 50, 7524.

23.    S: Mononuclear water oxidation catalysts, D. G. H. Hetterscheid, J. N. H. Reek, Angew. Chem., Int. Ed., 2012, anie.201202948

-          Patents

S: D.G.H. Hetterscheid; J. N. H. Reek, European patent EP11180779, filed September 9th 2011