Lipase Active‐Site‐Directed Anchoring of Organometallics: Metallopincer/Protein Hybrids

Kruithof, Cornelius A.; Casado, Miguel; Guillena, Gabriela; Egmond, Maarten R.; Hoof, Anca van der Kerk-van; Heck, Albert J. R.; Gebbink, Robertus J. M. Klein; Koten, Gerard van

doi:10.1002/chem.200500671

Cited by 95 publications

(71 citation statements)

References 56 publications

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“…Ample evidence has been gathered to show that catalytic properties of the pincer complex can be affected via the nature of the Z-substituent [2,11,12]. Furthermore, Z can be used to attach tethering groups which are suited to immobilize pincer-metal complexes to various supports, like polymers [3,[13][14][15], silica [16][17][18], dendrimers [19,20], and bucky-balls [21], or peptides [6,22], and enzymes [23].…”

Section: Ece-pincer Metal Complexes [Mx(ece-z)l N ] (Ece-z = [C 6 H 2mentioning

confidence: 99%

Self-assembly of para-OH functionalized ECE-metalated pincer complexes

Mehendale

Lutz

Spek

et al. 2008

Journal of Organometallic Chemistry

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a b s t r a c tVarious para-OH functionalized ECE-pincer metal complexes [MX(ECE-OH)L n ] (ECE-OH = [C 6 H 2 (CH 2 E) 2 -2,6-OH-4] À , E = NMe 2 , PPh 2 and SPh) were synthesized. The X-ray crystal structures of neutral [PdCl(SCS-OH)], [PdCl(NCN-OH)], and cationic [Pd(PCP-OH)(MeCN)](BF 4 ) are reported. The neutral halide complexes exhibit self-assembly to form polymeric chains via H-bonding involving the para-OH group as donors and the halide ligand on the metal as acceptors. Moreover, the halide ligand can be replaced by a monomeric aryloxy-O ligand leading to the formation of a covalently bonded dimer. The crystal structure of such a dimer derived from [PdI(NCN-OH)] is reported. Furthermore, these pincer-metal complexes were tethered through a carbamate linker to a siloxane functionality with the aim to be immobilized on a silica support. The crystal structure of a siloxane-functionalized [PtI(NCN-Z)] complex exemplifies how other H-bonding interactions not involving the metal-halide groupings can lead to polymeric networks as well.

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Section: Ece-pincer Metal Complexes [Mx(ece-z)l N ] (Ece-z = [C 6 H 2mentioning

confidence: 99%

Self-assembly of para-OH functionalized ECE-metalated pincer complexes

Mehendale

Lutz

Spek

et al. 2008

Journal of Organometallic Chemistry

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“…To our delight, covalent, stereoselective anchoring of a pincer metal catalyst in the active site of serine hydrolases, by its inhibition, appeared possible [67]. To this end, a tether ending in a para- nitrophenyl phosphonate ester group was installed at the paraposition of the parent pincer metal compound.…”

Section: Proof-of-principlementioning

confidence: 99%

Highlights of 45 years of research: A personal account

Koten

2017

Journal of Organometallic Chemistry

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a b s t r a c tThis part of my biosketch, which I prepared on invitation by the Editors, made me realize again how entangled my interest for doing research and teaching and management have been over the years. Working together with my students and colleagues has always been a strong motivation and pleasure for me and I hope that this sketch of our research reflects our common enthusiasm for what we achieved.In hindsight, trying to overlook almost 45 years of research, various main themes can be discerned that marked my fundamental research in the subsequent periods at TNO Utrecht (1968e1977), University of Amsterdam (1977e1986) and University of Utrecht (1986e2007). Overarching has been my preference and fascination for working with nitrogen based ligands (culminating in the design and use of the NCNpincer ligand platform, vide infra), the study of synthetic routes for organometallics (most importantly trans-and cyclo-metallation routes), the use of NMR for the study of the stereochemistry of organometallics (cf. the early use of 107,109 Ag NMR for detecting and following the formation of coordination compounds with helical structures), chemistry involving organometallic radicals (cf. organozinc and aluminum a-diimine chemistry, development of b-lactam synthesis routes), self-assembly of organometallics to discrete aggregated species (cf. organo-Cu, -Li and cuprate chemistry), the development of palladium complexes and homogeneous metal catalysts with simple amine ligands, the synthesis of, and catalysis with, dendrimers decorated with organometallic catalysts, mimicking the active center of metallo-enzymes as well as the synthesis of organometal-lipase hybrids for catalysis.Being educated in an "eco"-system of contract research, in concert with fundamental research, the results of the above outlined items were not only published in journals with peer review (>850) but also in the patent literature (>40). Most important were the results reported in over 85 PhD theses that I had the privilege to supervise as PI. The references refer to key-papers describing this body of work. The respective reference numbers are given at the heading of each paragraph. The full list of publications in peer reviewed Journals can be found in http://www.gerardvankoten.nl and www.uu.nl/staff/GvanKoten.© 2017 The Author. Published by Elsevier B.V. This is an open access article under the CC BY license (http://creativecommons.org/licenses/by/4.0/). GeneralAs indicated above, nitrogen ligands fascinated me throughout my research career, right from the very beginning. Whereas in my early days ligands with phosphorous donor atoms were the dominating "privileged" ligands in inorganic and organometallic chemistry; they have remained so up until now. However, my interest for nitrogen-containing ligands was fortified for a number of reasons; i, Nitrogen is one of the smallest donor atoms. This results in short N-metal bond distances thus affecting/interfering with its (N)R-substituents (also because of the short N-C bonds, viz. N-cone angle c...

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“…Metal-complex attachment on support surfaces enables such unsaturated active metal complexes to remain on oxide surfaces. 23,25,32,33 …”

Section: Surface-mediated Design Of Catalytically Activementioning

confidence: 99%

“…Metal-complex attachment on support surfaces enables such unsaturated active metal complexes to remain on oxide surfaces. 23,25,32,33 A novel 3-coordinated unsaturated Ru complex can be prepared on the surface of SiO 2 by the exothermic reaction induced selective elimination of a p-cymene ligand in an immobilized Rup-cymene complex. A Ru precursor complex, a monomeric p-cymene-coordinated RuN-sulfonyl-1,2-ethylenediamine complex (A), 34 was tethered on SiO 2 .…”

Section: Surface-mediated Design Of Catalytically Activementioning

confidence: 99%

Surface-Mediated Design and Catalytic Properties of Active Metal Complexes for Advanced Catalysis Creation

Tada¹

2010

Bulletin of the Chemical Society of Japan

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Molecular-scale design of catalytically active structures at oxide surfaces is highlighted, focusing on our recent challenges for selective heterogeneous catalysis. We found novel structural transformations of supported metal complexes on oxide surfaces and achieved unique selective catalysis for various chemical syntheses. In this account, the advanced design of supported metal-complex catalysts on oxide surfaces and the in situ characterization of their structural kinetics, which means kinetics of structural changes of catalysts themselves, under catalyst-working conditions are reviewed. Surface-Mediated Design of Catalytically ActiveStructures for Selective Catalysis 1.1 Introduction: Metal-Complex Attaching on Oxide Surfaces. Heterogeneous solid catalysts have been widely utilized for the industrial production of many synthetic chemicals. The advantages of heterogeneous catalysts are not only the separation of catalysts and products from reaction media but also their high durability and catalytic activities resulting from the unique structures of catalytically active sites at solid surfaces. Relationships among the metal structures, organized environment, and the catalytic properties of surface species tell us the nature of catalysis and new strategy for rational design of heterogeneous catalysts.Metal-complex attachment to oxide surfaces is a practical way to produce molecularly regulated structures of active metal species on oxide surfaces, and subsequent structural transformation in a controllable manner often provides unique regulated metal structures active for selective catalytic reactions. 116 There are several types of metal-complex attachment techniques: coordination of metal-complex precursors to immobilized ligands on organic polymers, 1721 coordination of metal-complex precursors to functional ligands bound to oxide surfaces, 2,4,2225 intercalation into clay materials, 26 ion exchange into porous materials such as zeolite and mesoporous silica, 27 and direct attachment of metal-complex precursor onto oxide surfaces. 3,6,11,28,29 The interfacial attachment between a metal complex and an oxide surface can produce unique metal coordination different from the original metal-complex precursor. For example, SiOH is reacted with a M(CH 3 ) complex and a M(OSi) complex is produced, releasing CH 4 . A chemical bond between a metal-complex precursor and a support surface modifies the reactivity of the supported metal complex, resulting in novel catalytic activity the precursor complex does not exhibit. 3,6,11,28,29 Traditional ion-exchange on zeolites and intercalation to clay materials are also typical ways to introduce metal species onto solid supports although the valences and types of metal precursors are restricted. 4 Direct reactions of metal-complex precursors and hydroxy groups on oxide surfaces create novel metal-coordination structures, and many important factors for selective catalysis can be controlled at the interface, such as electronic properties and coordination sphere of the attached metal...

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Lipase Active‐Site‐Directed Anchoring of Organometallics: Metallopincer/Protein Hybrids

Cited by 95 publications

References 56 publications

Self-assembly of para-OH functionalized ECE-metalated pincer complexes

Self-assembly of para-OH functionalized ECE-metalated pincer complexes

Highlights of 45 years of research: A personal account

Surface-Mediated Design and Catalytic Properties of Active Metal Complexes for Advanced Catalysis Creation

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