Bas de Bruin’s Research Group

- Short CV

- Research

- Sponsors

- Non-refereed Publications, Editorials & Interviews

- Refereed Publications

Contact

Dr. B. (Bas) de Bruin

Universiteit van Amsterdam

Faculty of Science,

van 't Hoff Institute for Molecular Sciences,

Homogeneous and Supramolecular Catalysis Group

Science Park 904, 1098 XH Amsterdam.

The Netherlands

Room E1.48

Tel: +31 20 525 6495

E-mail: b.debruin@uva.nl

Research

The sub-group of Bas de Bruin aims at understanding and developing (new) homogeneous catalytic reactions. Catalytic topics include late transition metal catalyzed olefin (ep)oxidation, hydrogenation, cyclopropanation and other carbene transfer reactions, aziridination and carbene polymerisation reactions. The group increasingly focuses at the development of new functional (polymeric) materials from carbene sources. Detailed insights are gathered through a combination of synthetic modelling, DFT calculations, EPR and NMR spectroscopy, applied catalysis and kinetic investigations. Experimental results are combined with DFT calculations, not only to obtain deeper insights in the intimate mechanisms but also to search for new transition-state analogies among reactions. Such TS analogies are used to disclose new possibilities for novel catalytic reactions, which are further explored in target-oriented test reactions. The use of unconventional ligands (e.g. “hard” N-donors for “soft” Rh, and so-called “redox non-innocent” and “cooperative” ligands) and metals in unconventional oxidation states is further expected to create new reactivity and more diversity in the ‘organometallic playground’ of catalysis. The group currently focuses on the following research topics:

- Oxidation Reactions

- Reactive, ‘Redox Non-Innocent’ & Cooperative Ligands in Catalysis

- Reactivity of Organometallic Radicals

- Catalytic Carbene Insertion Reactions (Carbene Polymerization)

Oxidation Reactions

Synthetic modelling to gain a better understanding of catalysis has been, and still is, an actively pursued research theme by Bas de Bruin and his research team. Especially in the field of Rh mediated olefin oxygenation synthetic models have provided many new mechanistic insights (Angew. Chem. 1997, 1999, 2002; Chem. Eur. J. 1999, 2000, 2001) and new catalytic reactions (Organometallics 2004).

The investigations aim at gaining improved understanding of rhodium- and iridium mediated olefin oxygenation with O₂ and H₂O₂ (very different from Pd based Wacker oxidation in many aspects) through structural and spectroscopic characterization of species that had previously only been postulated as intermediates. Examples of such uncovered intermediates include 2‑metallaoxetanes, metalladioxolanes, peroxo-olefin complexes, and many more. Screening of the reactivity of the thus obtained ‘candidate intermediates’, revealed a rich chemistry. A detailed overview is presented in a review (Angew. Chem. 2004).

This project is sponsored by the Netherlands Organisation for Scientific Research (NWO).

Reactive, ‘Redox Non-Innocent’ & Cooperative Ligands in Catalysis

In this project we aim at developing new catalytic approaches for challenging (new) reactions in homogeneous transition metal catalysis research. These investigations involve the use of redox non‑innocent and cooperative ligands to achieve challenging catalytic transformations. The cooperative ligand is not just a spectator ligand, but actively participates in bond making and bond breaking processes in converting substrates to products (JACS 2008, Chem. Eur. J. 2008, Organometallics 2010, JACS 2010). This topic is pursued in close collaboration with the groups of Grützmacher (ETH), Zhang (U South Florida) and Tejel/Ciriano (Zaragoza). The project is co-sponsored by the Netherlands Organisation for Scientific Research (NWO) and the European Research Council (ERC)..

Reactivity of Organometallic Radicals

In the field of paramagnetic organometallic chemistry the group is currently working at the front-line of the competitive and internationally emerging new research field of metallo-radicals (Chem. Comm. 2002; Angew. Chem. 2002; JACS 2005 (2x); Dalton 2005; Organometallics 2002, 2003, 2004, 2005; Chem. Eur. J. 2007, EurJIC 2007, Progr. Inorg. Chem. 2007, JACS 2010, Angew. Chem. 2010). Radical-type reactivity of open-shell organometallic complexes is a largely uncharted research area. Increasing reports on their involvement in catalysis stimulated a world-wide interest in their properties. We reported the first example of an iridium(II)-ethene species, and since then our group reported on a variety of paramagnetic M⁰(olefin) and M^II(olefin) species (M = Rh, Ir, Co). EPR spectroscopy, in combination with DFT calculations, is used as a powerful technique to obtain detailed information about the electronic structure and reactivity of these species. Fascinating is that alkene and carbene ligands can bear almost the entire spin-population of the paramagnetic complex, which thus behave as “redox non-innocent” ligands. Such donor-induced shifting of spin-density from the metal to the ligand constitutes a fundamentally new approach to tune the reactivity of open-shell metal-olefin complexes, and plays a crucial role in the mechanism of cobalt-catalyzed olefin cyclopropanation reactions (Chem. Eur. J. 2008; JACS 2010). For a detailed overview of this developing and interesting research field, we refer to our recent review articles and highlights on this topic (Progr. Inorg. Chem. 2007; EurJIC 2007, Angew. Chem. 2011, Inorg. Chem. 2011). This topic is pursued in close collaboration with the groups of Grützmacher (ETH), Zhang (U South Florida), Tejel/Ciriano (Zaragoza) and Chan (Hong Kong). The project is co-sponsored by the Netherlands Organisation for Scientific Research (NWO) and the European Research Council (ERC).

Catalytic Carbene Insertion Reactions

Metallo-carbenes are well-known as important intermediates in olefin cyclopropanation and olefin metathesis reactions (Nobel-prize 2005), but more recently it has become clear that their chemistry is far richer. We recently demonstrated that metallo-carbenes can be used in transition metal insertion polymerization to arrive at completely new types of stereoregular carbon-chain polymers Notably these new polymers contain a polar functional side group at each carbon of the polymer backbone (JACS 2006). This new family of poly(substituted methylene) polymers has a tremendous potential for the development of new materials, which are easily modified to tune the material properties, for various possible applications (Chem. Soc. Rev. 2010).

We are now further investigating the mechanism (JACS 2007, Organometallics 2010, Dalton 2009) and scope (Macromolecules 2010) of this remarkable new reaction. We will use this new concept to prepare new polymeric materials based on homo- and co-polymerisation of (functionalized) carbenes, and we are investigating co-polymerisation of carbenes with other reactive monomers.

The obtained syndiotactic (co)polymers are highly crystalline, and reveal interesting thermotropic and lyotropic liquid crystalline properties (Macromolecules 2010).

This project is co-sponsored by the Netherlands Organisation for Scientific Research (NWO), the Dutch Polymer Institute (DPI) and the European Research Council (ERC).

In addition we are also trying to uncover new reactions in which carbene (migratory) insertion reactions play a central role. DFT calculations suggest that the transition state (TS) of the new carbene polymerisation reaction is very similar to the TS’s of a variety of carbonyl insertion reactions. Based on this analogy, we will investigate several new carbene insertion reactions, potentially leading to new and useful polymeric materials and new synthetic routes to prepare small functional organic molecules. Traditional ligand screening & modification methods and new combinatorial and supramolecular approaches (encapsulation) will be explored to arrive at new and improved catalyst. DFT calculations will assist in gaining deeper mechanistic insights required for the optimization of such new catalytic reactions.

Short CV

Bas de Bruin studied chemistry at the University of Nijmegen from 1989-1994. He obtained his Ph.D. (April 20, 1999) from the same university (Rh Mediated Olefin Oxygenation). He did his postdoc in the group of Wieghardt at the Max-Planck Institut für Bioanorganische Chemie (Mülheim a/d Ruhr, Germany, April 1999-April 2000) for which he obtained an Alexander-von-Humboldt fellowship in 1999. After his postdoc he returned to the University of Nijmegen as an assistant professor in Inorganic Chemistry (Metal-Organic Chemistry), where he was involved in several research activities ranging from olefin oxygenation, radical organometallic chemistry, EPR spectroscopy, catalysis, light-switchable redox bistable molecules, DFT calculations, and (catalytic) synthesis of new materials. September 2005, Bas de Bruin obtained a prestigious (national) NWO-VIDI grant to uncover new catalytic reactions which is currently pursued at the University of Amsterdam (UvA, Homogeneous and Supramolecular Catalysis group) where he currently holds an associate professor (UHD) position. Bas de Bruin presently focuses at the development of new tools in homogeneous catalysis, using metals in unconventional oxidation states and unconventional ligands, specifically aiming at the development of new catalytic reactions. In 2008 Bas de Bruin obtained a prestigious ERC Starting Grant (first round of the EU 7^th framework Ideas Program; ERC = European Research Council). In 2012 he obtained a prestigious NWO-VICI grant to investigate new controlled (catalytic) radical-type transformations. Bas de Bruin is involved in teaching Inorganic Chemistry, Thermodynamics, Organometallic Chemistry, Bioinorganic Chemistry, Homogeneous Catalysis and (Catalytic) Reaction Mechanisms.

Sponsors:

Non-Refereed Publications, Editorials & Interviews

10. Chemisch2weekblad (C2W) profiel Bas de Bruin (VICI highlight)

Kosterman, K.; de Bruin, B.; C2W. jrg 108, #3, Febr. 2012, p38.

9. Angewandte Chemie Author Profile Bas de Bruin

de Bruin, B., Angew. Chem. Int. Ed. 2012, 51, 1102.

8. Cooperative & Redox Non-Innocent Ligands in Directing Organometallic Reactivity

Hindson, K..& de Bruin, B., Eur. J. Inorg. Chem., 2012, 3, 340 – 342.

Editorial.

7. Antiferromagnetic interactions in a distorted cubane-type tetranuclear manganese cluster.

Kampert, E.; Russcher, J.C.; Boukhvalov, D.W.; Janssen, F.F.B.J.; Smits, J.M.M.; de Gelder, R.; de Bruin, B.;

Christianen, P.C.M.; Rowan, A.E.; Katsnelson, M.I.; Maan, J.C.; Zeitler, U.;

Journal of Physics: Conference Series, 2010, 200, 022022.

6. Electromeric Rhodium Radical Complexes (highlight of paper)

CHIMIA 2010, 64, No. 4, 266.

5. Chemisch2weekblad (C2W): Elektromeren in Evenwicht (highlight of 2 papers)

Dijkgraaf, A.; de Bruin, B.; C2W. jrg 106, #1, Jan. 2010, p9.

4. Highly functionalized polymers from carbenes by Rh-mediated polymerization of diazoesters.

Jellema, E.; Reek, J. N. H.; de Bruin, B.*; PMSE Preprints, 2009, 101, 1762 - 1763.

3. ERC subsidie Bas de Bruin en Sander Woutersen

Folia (weekblad voor de Universiteit van Amsterdam), jaargang 61, 14-03-2008, Nr 24, P. 24-25.

http://www.folia.nl/archief/jaargang_61/Folia24_61.pdf

2. Projects Magazine (Britisch Publishers) online profile (ERC Highlight)

http://viewer.zmags.com/publication/cc00a33c#/cc00a33c/1

1. Chemisch2weekblad (C2W) profiel Bas de Bruin (Jonge Chemici Highlight)

Van der Wilt, P.; de Bruin, B.; C2W. jrg 97, #23, Dec. 2001, p37.

Books & Book Chapters (Refereed & Non-Refereed)

2. Open-Shell Organometallics: Reactivity at the Ligand

Dzik, W.I.; de Bruin, B.* Specialist Periodical Report Organometallic Chemistry, 2011, volume 37, p.46 - 78.

Invited Review. Book Chapter (Non-Refereed).

1. The Organometallic Chemistry of Rh, Ir, Pd and Pt based Radicals; Higher Valent Species.

Hetterscheid, D.G.H.; Grützmacher, H; Koekoek, A.J.J.; de Bruin, B.*; Progress in Inorganic Chemistry, 2007, 55, 247 - 253.

Invited Review. Book Chapter (Refereed).

Patents & Patent applications

1. FUNCTIONALIZED MATERIALS BY CATALYZED CARBENE COPOLYMERIZATION

Jellema, E.; Jongerius, A.L.; Fransen, N.G.M.; de Bruin, B.; WO 2011/157444 A1; PCT/EP2011/003016.

International publication date: 22 December 2011.

Refereed Scientific Publications

In Press

99. Unraveling the Electronic Structures of Low-valent Naphthalene and Anthracene Iron Complexes: X-ray, Spectroscopic and DFT Studies

Schnöckelborg,E.-M.; Khusniyarov, M.M.; de Bruin, B.; Hartl, F.; Langer, T.; Eul, M; Schulz, S.; Pöttgen, R.; Wolf, R.; Inorg. Chem.. 2012, accepted.

98. Closed-Shell and Open-Shell Square-Planar Iridium Nitrido Complexes

Scheibel, M.G.; Askevold, B.; Heinemann, F.; Reijerse, E.J.; de Bruin, B.*; Schneider, S.*, Nature Chemistry, 2012, accepted.

97. Stereospecific Carbene Polymerisation with Oxygenated Rh(diene) Species

Walters, A.J.C.; Troeppner, O.; Ivanović-Burmazović, I.; Tejel, C.; del Río, M.P.; Reek, J.N.H.; de Bruin, B.*;

Angew. Chem. Int. Ed., 2012, accepted, DOI: 10.1002/anie.201200069.

96. Controlled Synthesis of Functional Copolymers with Blocky Architectures via Carbene Polymerization

Franssen,N.M.G.; Remerie, K.; Macko, T.; Reek, J.N.H.; de Bruin, B.*; Macromolecules., 2012, accepted,

DOI: http://dx.doi.org/10.1021/ma300314q

95. Chromatographic Examination of the Chemical Composition and Sequence Distribution of Copolymers from Ethyl and Benzyl Diazoacetate

Reingruber, E.M.; Chojnacka, A.; Jellema, E.; de Bruin, B.; Buchberger, W.; Schoenmakers, P.J.; Journal of Chromatography A, 2012, accepted.

2012

94. Highly selective asymmetric Rh-catalyzed hydroformylation of heterocyclic olefins

Chikkali, S.H.; Bellini,, R.; de Bruin, B.; van der Vlugt, J.I.; Reek, J.N.H.; J. Am. Chem. Soc. 2012, 134, 6607−6616.

93. Synthesis and Reactivity of Ester-Functionalized 5-Membered Rh^I-k²-C,O-Chelates and their Relevance in

Rh(cod)-Mediated Carbene Polymerization

Finger, M.; Lutz, M.; Reek, J.N.H.; de Bruin, B.*; Eur. J. Inorg. Chem. 2012, 9, 1437–1444.

Invited paper. Special Issue “Organometallic Chemistry”.

92. Ligand Denticity Controls Enantiomeric Preference in DNA-based Asymmetric Catalysis

Boersma, A. J.; de Bruin, B.; Feringa, B. L.; Roelfes, G.; Chem. Commun., 2012, 48, 2394–2396.

91. Redox Non-innocent Ligands – Versatile New Tools to Control Catalytic Reactions

Lyaskovskyy, V.; de Bruin, B.*, ACS Catalysis, 2012, 2, 270–279.

Invited Review.

90. Rh-Mediated Carbene Polymerization: From Multistep Catalyst Activation to Alcohol-Mediated Chain-Transfer

Walters, A. J. C.; Jellema, E. Finger, M.; Aarnoutse, P.; Smits, J. M. M.; Reek, J. N. H.; de Bruin, B.*, ACS Catalysis, 2012, 2, 246–260.

89. Snapshots of a Reversible Metal-Ligand Two-Electron Transfer Step Involving Compounds Related by Multiple Types of Isomerism

Tejel, C.; Asensio, L.; Pilar del Río, M.; de Bruin, B.; López, J. A.; Ciriano, M. A. Eur. J. Inorg. Chem. 2012, 3, 512 – 519.

Special Issue “Cooperative & Redox Non-Innocent Ligands in Directing Organometallic Reactivity”.

2011

88. Electronic Selectivity Tuning in Ti^III-Catalyzed Acetylene Cross-Dimerization Reactions

Oshovsky, G.V.*; Hessen, B.; Reek, J.N.H.; de Bruin, B.*; Organometallics, 2011, 30, 6067 ‑ 6070.

87. Developing Synthetic Approaches with Non-Innocent Metalloligands: Easy Access to Ir^I/Pd⁰ and Ir^I/Pd⁰/Ir^I cores

Tejel, C.; Asensio, L.; del Río, M. P.; de Bruin, B.; López, J. A.; Ciriano, M. A. Angew. Chem. Int. Ed. 2011, 50, 8839 – 8843.

86. Mechanism of Cobalt(II) Porphyrin-Catalyzed C−H Amination with Organic Azides: Radical Nature and H-Atom Abstraction Ability

of the Key Cobalt(III)-Nitrene Intermediates

Lyaskovskyy, V.; Olivos Suárez, A. I.; Lu, H.; Jiang, H.; Zhang, X. P.*; de Bruin, B.* J. Am. Chem. Soc. 2011, 133,12264 – 12273.

85. Experimental Evidence for Cobalt(III)-Carbene Radicals: Key Intermediates in Cobalt(II)-Based Metalloradical Cyclopropanation

Lu, H.; Dzik, W.I.; Xu, X;. Wojtas, L.; de Bruin, B.*; Zhang, X.P.* J. Am. Chem. Soc. 2011, 133, 8518 – 8521.

84. Pincer Ligands with an All-Phosphorus Donor Set: Subtle Differences between Rhodium and Palladium

Bauer, R.C.; Gloaguen, Y.; Lutz, M.; Reek, J.N.H.; de Bruin, B.; van der Vlugt, J.I., Dalton Trans., 2011, 40, 8822 – 8829.

83. Cooperative Double Deprotonation of Bis(2-picolyl)amine Leading to Unexpected Bimetallic Mixed Valence

(M^-I, M^I) Rhodium and Iridium Complexes

Tejel, C.*; del Río, M.P.; Asensio, L.; van den Bruele, F.J.; Ciriano, M.A.;Tsichlis i Spithas, N.; Hetterscheid, D.G.H.; de Bruin, B.*

Inorg. Chem. 2011, 50, 7524 - 7534.

82. The Radical Mechanism of Cobalt(II) Porphyrin-Catalyzed Olefin Aziridination and the Importance of Cooperative H-Bonding.

Olivos Suarez, A.I.; Jiang, H.; Zhang, X.P.*; de Bruin, B.*, Dalton Trans., 2011, 40, 5697 - 5705.

Inside Front Cover.

81. Open-shell Organometallic [M^II(dbcot)(bis-lutidylamine)]²⁺ complexes (M = Rh, Ir); Unexpected Base-Assisted Reduction

of the Metal instead of Amine Ligand Deprotonation.

Dzik, W.I.; Fuente, L.A., Siegler, M.A.; Spek, A.L.; Reek, J.N.H.; de Bruin, B.*, Organometallics, 2011, 30, 1902 - 1913.

80. The Redox Non-Innocence of Carbene Ligands: Carbene Radicals in (Catalytic) C-C Bond Formation

Dzik, W.I.; Zhang, X.P.*; de Bruin, B.*, Inorg. Chem., 2011, 50, 9896 – 9903.

Invited Forum paper. Forum Issue on ‘New Chemistry of Redox Active Ligands’.

79. The role of b-H elimination in Rh Mediated Carbene Insertion Polymerization.

Finger, M.; Reek, J.N.H.; de Bruin, B.*, Organometallics, 2011, 30, 1094 - 1101.

78. Carbene Insertion into Transition Metal-Carbon Bonds: New Tool for Catalytic C–C Bond Formation

Franssen, N.M.G. Walters, A.J.C.; Reek, J.N.H.; de Bruin, B.*, Catalysis Science & Technology, 2011, 1, 153 - 165.

‘Hot Article’. Front Cover.

77. Binuclear [(cod)(Cl)Ir(bpi)Ir(cod)]⁺ for Catalytic Water Oxidation.

Dzik, W.I.; Calvo, S.E.; Reek, J.N.H.; Lutz, M.; Ciriano, M.A.; Tejel, C.; Hetterscheid, D.G.H.; de Bruin, B.*;

Organometallics, 2011, 30, 372 - 374 (communication).

76. Amino Olefin Nickel(I) and Nickel(0) Complexes as Dehydrogenation Catalysts for Amine Boranes.

Vogt, M.; de Bruin, B.; Berke, H.; Trincado, M.; Grützmacher, H.; Chemical Science, 2011, 2, 723 - 727.

75. Remote Supramolecular Control of Catalyst Selectivity in the Hydroformylation of Alkenes.

Dydio, P.; Dzik, W.I.; Lutz, M. de Bruin, B.; Reek, J.N.H.; Angew. Chem. Int. Ed., 2011, 50, 396 - 400.

Hot Paper. Back cover.

74. Ligands that Store & Release Electrons during Catalysis.

Dzik, W.I.; van der Vlugt, J.I.; Reek, J.N.H.; de Bruin, B.*; Angew. Chem. Int. Ed., 2011, 50, 3356 – 3358.

Highlight.

73. Pd-Mediated Carbene Polymerisation: Activity of Palladium(II) versus Low-Valent Palladium.

Franssen, N.M.G.; Reek, J.N.H.; de Bruin, B.*; Polymer Chemistry, 2011, 2, 422 - 431.

Invited paper. Special Issue Emerging Researchers in Polymer Chemistry.

2010

72. Preparation, Characterization and Electronic Structure of Homoleptic Diphosphacyclobutadiene Complexes

[M(η⁴-P₂C₂R₂)₂]^x– (M = Fe, Co; x = 0, 1).

Wolf, R.; Ehlers, A.W.; Khusniyarov; M.M. Hartl, F.; de Bruin, B.; Long, G.J.; Grandjean, F.; Schappacher, F.M.; Pöttgen, R.;

Slootweg, J.C.; Lutz, M.; Spek, A.L.; Lammertsma, K.; Chem. Eur. J. 2010, 16, 14322 – 14334.

71. Rh-mediated Stereospecific Carbene Polymerization: From Homopolymers to Random and Block Copolymers.

Jellema, E.; Jongerius, A.L.; Alberda van Ekenstein, G.; Mookhoek, S.D.; Dingemans, T.J.; Reingruber, E.M.; Chojnacka, A.; Schoenmakers, P.J.

Sprenkels, R.; van Eck, E.R.H.; Reek, J.N.H.; de Bruin, B.*; Macromolecules, 2010, 43, 8892 - 8903.

70. ‘Carbene Radicals’ in Co^II(por)-Catalyzed Olefin Cyclopropanation.

Dzik, W.I.; Xu, X.; Zhang, X.P.; Reek, J.N.H.; de Bruin, B.*; J. Am. Chem. Soc., 2010, 132, 10891 - 10902.

69. Multitechnique Approach to Reveal the Mechanism of Copper(II)-Catalyzed Arylation Reactions.

Tromp, M.; van Strijdonck, G.P.F.; van Berkel, S.S. van den Hoogenband, A.; Feiters, M.C.; de Bruin, B.; Fiddy, S.G. van der Eerden,

A.M. J.; van Bokhoven, J.A.; van Leeuwen, P.W.N.M.; Koningsberger, D.C.; Organometallics, 2010, 29, 3085 - 3097.

68. Ureaphosphanes as Hybrid, Anionic or Supramolecular Bidentate Ligands for Asymmetric Hydrogenation Reactions.

Meeuwissen, J.; Detz, R.; Sandee, A. J.; de Bruin, B.; Siegler, M.A.; Spek, A.L.; Reek, J.N.H.; Eur. J. Inorg. Chem. 2010, 19, 2992 - 2997.

67. Versatile New C₃-Symmetric Tripodal Tetraphosphine Ligands; Structural Flexibility to Stabilize Cu^I and Rh^I Species and Tune Their Reactivity.

Wassenaar, J.; Siegler, M.A.; Spek, A.L.; de Bruin, B.; Reek, J.N.H.; van der Vlugt, J.I.; Inorg. Chem. 2010, 49, 6495 - 6508.

66. Rhodium-Catalyzed Asymmetric Hydroformylation with Taddol-Based IndolPhos Ligands.

Wassenaar, J.; de Bruin, B.; Reek, J.N.H.; Organometallics, 2010, 29, 2767 - 2776.

65. Ligand Design in Rh(diene)-Mediated "Carbene" Polymerization; Efficient Synthesis of High-Mass, Highly Stereoregular, and

Fully Functionalized Carbon-Chain Polymers.

Jellema, E.; Jongerius, A.L.; Walters, A.J.C.; Smits, J.M.M.; Reek, J.N.H.; de Bruin, B.*; Organometallics, 2010, 29, 2823 - 2826.

64. Phosphinoureas: Cooperative Ligands in Rhodium-Catalyzed Hydroformylation? On the Possibility of a Ligand-Assisted Reductive

Elimination of the Aldehyde.

Meeuwissen, J.; Sandee, A.J.; de Bruin, B.; Siegler, M.A.; Spek, A.L.; Reek, J.N.H.; Organometallics, 2010, 29, 2413 - 2421.

63. Rhodium(I) mediated arylation of aldehydes with arylboronic acids under base and water free conditions: A computational study.

Olivos Suarez, A.I.; Reek, J.N.H.; de Bruin, B.*; J. Mol. Cat. A: Chem., 2010, 324, 24 - 30.

Invited paper. Special issue on Computational Catalysis.

62. C1 polymerisation and related C-C bond forming 'carbene insertion' reactions.

Jellema, E.; Jongerius, A.L.; Reek, J.N.H.; de Bruin, B.*; Chem. Soc. Rev., 2010, 39, 1706 - 1723.

Invited Review.

61. Carbonyl Complexes of Rhodium with N-Donor Ligands: Factors Determining the Formation of Terminal versus Bridging Carbonyls.

Dzik, W.I.; Creusen, C.; de Gelder, R.; Peters, T.P.J.; Smits, J.M.M.; de Bruin, B.*; Organometallics, 2010, 29, 1629 - 1641.

60. Activation of H₂ by a highly distorted Rh^II complex with a new C₃-symmetric tripodal tetraphosphine ligand.

Wassenaar, J.; de Bruin, B.; Siegler, M.A.; Spek, A.L.; Reek, J.N.H.; van der Vlugt, J.I.; Chem. Comm., 2010, 46, 1232 - 1234.

59. Highly enantioselective hydroformylation of dihydrofurans catalyzed by hybrid phosphine-phosphonite rhodium complexes.

Chikkali, S.H.; Bellini, R.; Berthon-Gelloz, G.; van der Vlugt, J.I.; de Bruin, B.; Reek, J.N.H.; Chem. Comm., 2010, 46, 1244 - 1246.

58. Rhodium-P,O-bidentate coordinated ureaphosphine ligands for asymmetric hydrogenation reactions.

Meeuwissen, J.; Detz, R.J.; Sandee, A.J.; de Bruin, B.; Reek, J.N.H.; Dalton Trans, 2010, 39, 1929 - 1931.

57. Electromeric Rhodium Radical Complexes.

Puschmann, F.F.; Harmer, J.; Stein, D.; Ruegger, H.; de Bruin, B.*; Grützmacher, H.*; Angew. Chem. Int. Ed., 2010, 49, 385 - 389. 

Highlighted in Nature Chemistry (Bally, T.; Nature Chemistry, 2010, 2, 165-166), C2W, and Chimia (CHIMIA, 2010, 64(4), 266)

56. P-C dichotomy: divergent iron(-I)-mediated alkyne and phosphaalkyne cycloligomerisations.

Wolf, R., Ghavtadze. N., Weber, K., Schnockelborg, E.M.; de Bruin, B., Ehlers, A.W.; Lammertsma, K.; Dalton Trans., 2010, 39, 1453 - 1456.

55. Rhodium(0) Metalloradicals in Binuclear C-H Activation.

Puschmann, F.F.; Grützmacher, H.*; de Bruin, B.*, J. Am. Chem. Soc., 2010, 132, 73 - 75. (communication).

2009

54. Ligand-Controlled Magnetic Interactions in Mn₄ Clusters.

Kampert, E.; Janssen, F.F.B.J.; Boukhvalov, D.W.; Russcher, J.C.; Smits, J.M.M.; de Gelder, R.; de Bruin, B.*; Christianen, P.C.M.; Zeitler, U.*;

Katsnelson, M.I.; Maan, J.C.; Rowan, A.E.* Inorg. Chem., 2009, 48, 11903 - 11908.

53. Ligand Centred Reactivity of Bis(picolyl)amine Iridium; Sequential Deprotonation, Oxidation and Oxygenation of a ‘Non-Innocent’ Ligand.

Tejel, C.*; del Río, M.P.; Ciriano, M.A.; Reijerse, E.J.; Hartl, F.; Záliš, S.; Hetterscheid, D.G.H.; Tsichlis i Spithas, N.; de Bruin, B.*;

Chem. Eur. J, 2009, 15, 11878 - 11889.

52. Supramolecular NHC ligands: On the influence of Zn^II-templates on the activity of Rh^I(cod) complexes in ‘Carbene Polymerization’.

Rubio, M.; Jellema, E.; Siegler, M.A.; Spek, A.L.; Reek, J.N.H.*; de Bruin, B.*; Dalton Trans., 2009, 41, 8970 - 8976.

Invited Paper. Themed Issue: Metal Catalyzed Polymerisation

51. Water Splitting by Cooperative Catalysis.

Hetterscheid, D. G. H;. van der Vlugt, J. I.; de Bruin, B.; Reek, J. N. H.; Angew. Chem. Int. Ed., 2009, 48, 8178 - 8181.

50. Hydrogen-Atom Transfer in Reactions of Organic Radicals with [Co^II(por)]. (por=Porphyrinato) and in Subsequent Addition of [Co(H)(por)] to Olefins.

de Bruin, B.*; Dzik, W.I.; Li, S.; Wayland, B.B.* Chem. Eur. J., 2009, 15, 4312 - 4320.

49. Structure and Reactivity of a Unique Y-Shaped Tricoordinate Bis(silyl)platinum(II)-NHC Complex.

Berthon-Gelloz, G.; de Bruin, B.; Tinant, B.; Marko, I.E. Angew. Chem. Int. Ed., 2009, 48, 3161 - 3164.

48. A Phosphorus Analogue of Bis(h⁴-cyclobutadiene)iron(0).

Wolf, R.; Slootweg, J.C.; Ehlers, A.W.; Hartl, F.; de Bruin, B.; Lutz, M.; Spek, A.L.; Lammertsma, K.;

Angew. Chem. Int. Ed., 2009, 48, 3104 - 3107.

Front Cover.

47. Sulfonamido-Phosphoramidite Ligands in Cooperative Dinuclear Hydrogenation Catalysis.

Patureau, F.W.; de Boer, S.; Kuil, M.; Meeuwissen, J.; Breuil, Pierre-Alain R.; Siegler, M.A.; Spek, A.L.; Sandee, A.J.;

de Bruin, B.; Reek, J.N.H.; J. Am. Chem. Soc., 2009, 131, 6683 - 6685.

46. Activation of Carbon Monoxide by (Me₃tpa)Rh and (Me₃tpa)Ir.

Dzik, W.I.; Smits, J.M.M.; Reek, J.N.H.; de Bruin, B.*; Organometallics, 2009, 28, 1631 - 1643.

2008

45. Intervalent bis(m-aziridinato)M^II-M^I complexes (M = Rh, Ir): delocalized metallo-radicals or delocalized aminyl radicals?

Tejel, C.*; Ciriano, M.; Passarelli, V.; Lopez, J.A.; de Bruin, B.*; Chem. Eur. J., 2008, 14, 10985 - 10998.

44. Ligand oxidation of a deprotonated bis(picolyl)amine Ir^I(cod) complex.

Tejel, C.*; Ciriano, M.A.; del Rio, M.P.; Hetterscheid, D.G.H.; Tsichlis i Spithas, N.; Smits, J.M.M; de Bruin, B.*;

Chem. Eur. J., 2008, 14, 10932 - 10936 (Communication).

43. Exchange of Organic Radicals with Organo-Cobalt Complexes Formed in the Living Radical Polymerization of Vinyl Acetate.

Li, S.; Peng, C.-H.; Fryd, M.; Wayland, B. B.*; de Bruin, B.*; J. Am. Chem. Soc., 2008, 130, 13373 - 13381.

42. Selective C-C Coupling of ‘Ir(ethene)’ and ‘Ir(Carbenoid)’ Radicals.

Dzik, W.I; Reek, J.N; de Bruin, B.*, Chem. Eur. J., 2008, 14, 7594 - 7599.

41. 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; M.A. del Río; M.P. van den Bruele, F.J.; Hetterscheid, D.G.H.; Tsichlis i Spithas, N.; de Bruin, B.*;

J. Am. Chem. Soc., 2008, 130, 5844 - 5845.

40. Carbon-Carbon Bond Activation of TEMPO by a Rh^II Metallo-Radical: A Combined Experimental and Theoretical Study.

Chan, K.-S; Li, X.Z; Dzik, W.I; de Bruin, B.*; J. Am. Chem. Soc, 2008, 130, 2051 - 2061.

2007

39. Rh Mediated Polymerization of Carbenes: Mechanism and Stereoregulation.

Jellema, E.; Budzelaar, P.H.M.; Reek, J.N.H.; de Bruin, B.*; J. Am. Chem. Soc., 2007, 129, 11631 - 11641.

37. Spin density distribution in mononuclear Rh(0) complexes: A combined experimental and DFT study.

de Bruin, B.*; Russcher, J.C.; Grützmacher, H.*; J. Organomet. Chem. 2007, 692, 3167 - 3173.

Invited paper (Special Issue about “One-electron Reactivity in Organometallic Chemistry“).

36. Unusual Stereochemistry in complexes of the form [RhH(CO)₂(PⁱPr₃)].

Cheliatsidou, P.; White, D.F.S.; de Bruin, B.; Reek, J.N.H.; Cole-Hamilton, D.J.; Organometallics, 2007, 26, 3265 - 3268.

35. Hydrogen-Atom Transfer in Open-Shell Organometallic Chemistry: The Reactivity of Rh^II(cod) and Ir^II(cod) Radicals.

Hetterscheid, D.G.H.; Klop, M.; Kicken, R.J.N.A.M; Smits, J.M.M.; Reijerse, E.J.; de Bruin, B.*; Chem. Eur. J., 2007, 13, 3386 - 3405.

34. Paramagnetic (alkene)Rh and (alkene)Ir complexes: metal or ligand radicals?

de Bruin, B.*; Hetterscheid, D.G.H.; Eur. J. Inorg. Chem., 2007, 2, 211 - 230.

Invited review.

2006

33. Rhodium-Mediated Stereoselective Polymerization of “Carbenes”.

Hetterscheid, D.G.H.; Hendriksen, C. Dzik, W.I.; Smits, J.M.M.; van Eck, E.R.H.; Rowan, A.E.; Busico, V.; Vacatello,

M.; Van Axel Castelli, V.; Segre, A.; Jellema, E.; Bloemberg, T.G.; de Bruin, B.*; J. Am. Chem. Soc., 2006, 128, 9746 - 9752.

Highlighted in Angewandte Chemie (A.F. Noels, Angew. Chem. Int. Ed. 2007, 46, 1208 – 1210.)

32. Dynamic combinatorial chemistry: the unexpected choice of receptors by guest molecules.

de Bruin, B.; Hauwert, P.; Reek, J. N. H.; Angew. Chem. Int. Ed., 2006, 45, 2660 - 2663.

31. Gas-Phase Reactivity of an Iridium(I) Complex with Dioxygen –Comparison to Solution Phase Reactivity.

Thewissen, S.; Plattner, D.A.; de Bruin, B.; Int. J. Mass Spec., 2006, 249/250, 446 - 450.

30. Open-Shell Rhodium and Iridium Species in (Catalytic) Oxygenation Reactions.

Hetterscheid, D.G.H.; de Bruin, B.*, J. Mol. Catal. A, Chemical, 2006, 251, 291 - 296.

2005-2002 (Assistant professor RU Nijmegen)

29. Formation of a paramagnetic Al complex and extrusion of Fe during the reaction of (diiminepyridine)Fe with AlMe₃ (R= Me,Et).

Scott, J.; Gambarotta, S.; Korobkov, I.; Knijnenburg, Q.; de Bruin, B.; Budzelaar, P.H.M.; J. Am. Chem. Soc., 2005, 127,17204 - 17206.

28. Instability of square planar N₃-ligand Iridium(I) ethene complexes.

Thewissen, S.; Reijnders, M.D.M.; Smits, J.M.M.; de Bruin, B.*; Organometallics, 2005, 24, 5964 - 5972.

27. Ir^II(ethene): Metal or Carbon Radical? Part II: Oxygenation via Iridium or Direct Oxygenation at Ethene?

Hetterscheid, D.G.H.; Bens, M.; de Bruin, B.*; Dalton Trans., 2005, 5, 979 - 984.

26. Olefin hydrogenation using diimine pyridine complexes of Co and Rh.

Knijnenburg, Q.; Horton,A.D.; van der Heijden, H. Kooistra, T.M.; Hetterscheid, D.G.H.; Smits, J.M.M.; de Bruin, B.;

Budzelaar, P.H.M, Gal, A.W.; J. Mol. Catal. A, Chemical, 2005, 232, 151 - 159.

25. Ir^II(ethene); Metal or Carbon Radical?

Hetterscheid, D.G.H.; Kaiser, J.; Reijerse, E.; Peters, T.P.J.; Thewissen, S.; Blok, A.N.J.; Smits, J.M.M.; de Gelder, R.;

de Bruin, B.*; J. Am. Chem. Soc., 2005, 127, 1895 - 1905.

24. Chloride-triggered disproportionation of a mononuclear Rh^II(nbd) species to Rh^I(nbd) and Rh^III(h¹-norbornenyl) complexes:

Possibilities for Wacker type mono-oxygenation of norbornadiene to norbornenone.

Hetterscheid, D.G.H.; Smits, J.M.M.; de Bruin, B.*; Organometallics, 2004, 23, 4236 - 4246.

23. Functional models for rhodium-mediated olefin oxygenation.

de Bruin, B.*; Budzelaar, P.H.M.; Gal, A.W.; Angew. Chem. Int. Ed., 2004, 43, 4142 - 4157.

Invited Review.

22. Etching AlAs with HF for epitaxial lift-off applications.

Voncken, M.M.A.J.; Schermer, J.J.; van Niftrik A.T.J.; Bauhuis, G.J.; Mulder, P.; Larsen, P.K.; Peters, T.P.J.; de Bruin, B.;

Klaassen, A.; Kelly, J.J.; J. Electrochem. Soc., 2004, 151, G347 - G352.

21. 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, D.G.H.; de Bruin, B.*; Smits, J.M.M.; Gal, A.W.; Organometallics, 2003, 22, 3022 - 3024.

20. Cobalt chloride complexes of N₃ and N₄ donor ligands.

Kooistra T.M.; Hekking K.F.W.; Knijnenburg Q; de Bruin B; Budzelaar P.H.M.; de Gelder R; Smits J.M.M.; Gal A.W.;

Eur. J. Inorg. Chem., 2003, 4, 648 - 655.

19. Formation of ethylene bridged dinuclear Ir^III species via coupling of Ir^II and Ir^II(ethene).

de Bruin, B.*; Thewissen, S.; Yuen, T.-W.; Peters, T.P.J.; Smits, J.M.M.; Gal, A.W.; Organometallics, 2002, 21, 4312 - 4314.

18. Dioxygenation of sterically hindered Rh^I- and Ir^I-ethene complexes to peroxo- and peroxo-ethene complexes.

de Bruin, B.*; Peters, T.P.J.; Wilting, J.B.M.; Thewissen, S.; Smits, J.M.M.; Gal, A.W.; Eur. J. Inorg. Chem., 2002, 10, 2671 - 2680.

17. Amido-bridged dinuclear rhodium(I) complexes by deprotonation of mononuclear rhodium(I) amine complexes.

de Bruin, B.; Peters, T.P.J.; Suos, N.F.A.; de Gelder, R.; Smits, J.M.M.; Gal, A.W.; Inorg. Chim. Acta., 2002, 337, 154 - 162.

16. Dioxygen activation by an unprecedented mononuclear Ir^II-ethene complex.

de Bruin, B.*; Peters, T.P.J.; Thewissen, S.; Blok, A.N.J.; Wilting, J.B.M.; de Gelder, R.; Smits, J.M.M.; Gal, A.W.;

Angew. Chem. Int. Ed., 2002, 41, 2135 - 2138.

15. Spontaneous disproportionation of rhodium(I) bisoxazolinates to rhodium(II).

Willems, S.T.H.; Russcher, J.C.; Budzelaar, P.H.M.; de Bruin, B.; de Gelder, R.; Smits, J.M.M.; Gal, A.W.; Chem. Commun., 2002, 148 - 149.

14. New routes toward metallated methanofullerene terdentate bisaminoaryl ligands.

Meijer, M.D.; Klink, G.P.M. van; de Bruin, B.; van Koten, G.; Inorg. Chim. Acta, 2002, 327, 31 - 40.

2001-1993 (Undergraduate, PhD and postdoc research)

13. Metal-to-ligand electron transfer in diiminopyridine complexes of Mn-Zn - a theoretical study.

Budzelaar, P.H.M.; de Bruin, B.; Gal, A.W.; Wieghardt, K.E.; van Lenthe, J.H.; Inorg. Chem., 2001, 40, 4649 - 4655.

12. Synthesis, Aggregation, and Binding Behaviour of Synthetic Amphiphilic Receptors.

Schenning, A.P.H.J.; Escuder, B.; van Nunen, J.L.M.; de Bruin, B.; Loewik, D.W.P.M.; Rowan, A.E.; van der Gaast, S.J.;

Feiters, M.C.; Nolte, R.J.M.; J. Org. Chem., 2001, 66, 1538 - 1547.

11. Enhanced Reactivity of 2‑Rhodaoxetanes Through a Labile Acetonitrile Ligand.

de Bruin, B.; Verhagen, J.A.W.; Schouten, C.H.J.; Gal, A.W.; Feichtinger, D.; Plattner, D.A.; Chem. Eur. J., 2001, 7, 416 - 422.

10. Molecular and Electronic Structures of Bis(pyridine-2,6-diimine)metal Complexes [ML₂](PF₆)_n (n = 0, 1, 2, 3; M = Mn, Fe, Co, Ni, Cu, Zn).

de Bruin, B.; Bill, E.; Bothe, E.; Weyhermueller, T.; Wieghardt, K.; Inorg. Chem., 2000, 39, 2936 - 2947.

9. 2-Rhodaoxetanes: Their Formation by Oxidation of [Rh^I(ethene)]⁺ and Their Reactivity upon Protonation.

de Bruin, B.; Boerakker, M.J.; Verhagen, J.A.W.; de Gelder, R.; Smits, J.M.M.; Gal, A.W.; Chem. Eur. J., 2000, 6, 298 - 312.

8. Selective Oxidation of [Rh^I(cod)]⁺ by H₂O₂ and O₂.

de Bruin, B.; Brands, J.A.; Donners, J.J.J.M., Donners, M.P.J., de Gelder, R.; Smits, J.M.M.; Gal, A.W.; Spek, A.L.; Chem. Eur. J., 1999, 5, 2921 - 2936.

7. Diversity in Complexation of [Rh^I(cod)]⁺ and [Ir^I(cod)]⁺ by Pyridine-Amine-Pyrrole Ligands.

de Bruin, B.; Kicken, R.J.N.A.M.; Suos, N.F.A., Donners, M.P.J., den Reijer, C.J.; Sandee, A.J.; de Gelder, R.; Smits, J.M.M.;

Gal, A.W.; Spek, A.L.; Eur. J. Inorg. Chem., 1999, 1581 - 1592.

6. Amidation of [Rh^I(ethene)]⁺ by H₂O₂/Acetonitrile via a 2-Rhodaoxetane.

de Bruin, B.; Boerakker, M.J.; de Gelder, R.; Smits, J.M.M.; Gal, A.W.; Angew. Chem. Int. Ed., 1999, 38, 219 - 222;

Angew. Chem., 1999, 111, 118 - 121.

5. Mono- and Di-nuclear Carbonyl Complexes of (1,4,7-Trimethyl-1,4,7-triazacyclononane)rhodium(I): Facile Migration of

a C(O)OMe Ligand at a Dinuclear Rh(m-CO)₂Rh Core.

de Bruin, B.; Donners, J.J.J.M.; de Gelder, R.; Smits, J.M.M.; Gal, A.W.; Eur. J. Inorg. Chem., 1998, 3, 401 - 406.

4. Oxidation of Rh^I(olefin) Fragments to 2‑Rhodaoxetanes.

de Bruin, B.; Boerakker, M.J.; Donners, J.J.J.M.; Christiaans, B.E.C.; Schlebos, P.P.J.; de Gelder, R.; Smits, J.M.M.; Spek, A.L.; Gal, A.W.;

Angew. Chem. Int. Ed. Engl., 1997, 36, 2063 - 2067; Angew. Chem., 1997, 109, 2153 - 2157.

3. Strong Binding of Paraquat and Polymeric Paraquat Derivatives by Basket-Shaped Hosts.

Schenning, A.P.H.J.; de Bruin, B.; Rowan, A.E.; Kooiman, H.; Spek, A.L.; Nolte, R.J.M.;

Angew. Chem. Int. Ed. Engl., 1995, 34, 2132 - 2134; Angew. Chem. 1995, 107, 2288 - 2289.

2. Molecular golfballs: Vesicles from bowl-shaped host molecules.

Schenning, A.P.H.J.; de Bruin, B.; Feiters, M.C.; Nolte, R.J.M.; Angew. Chem. Int. Ed. Engl. 1994, 33, 1662-1663; Angew. Chem., 1994, 106, 1741 - 1742.

1. Bridging CH₂ addition to the disulfur ligands of an iron-sulfur cluster compound.

Berg, W. van den; Linden, J.G.M. van der; Riessen, B.A. van; de Bruin, B.; Bosman, W.P.; Smits, J.M.M.; Beurskens, P.T.; Inorg. Chem., 1993, 32, 3637 - 3639.