A “Dendritic Effect” in Homogeneous Catalysis with Carbosilane-Supported Arylnickel(II) Catalysts:  Observation of Active-Site Proximity Effects in Atom-Transfer Radical Addition

Koten, Gerard van; Kleij, Arjan W.; Gossage, Robert A.; Gebbink, Robertus J. M. Klein; Brinkmann, N.; Reijerse, Edward J.; Kragl, Udo; Lutz, Martin; Spek, Anthony L.

doi:10.1021/ja0026612

Cited by 214 publications

(119 citation statements)

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“…Deactivation of the soluble G 1 -Ni 12 pincer catalyst during the Kharasch addition reaction was not observed most likely because of sufficient separation between the Ni centers. In later designs, the NCN-pincer Ni catalysts were: i. directly attached to the CS-dendrimer surface by covalent C-Si bonding to exclude unintentional loss of catalytic sites, ii, the coverage of the dendrimer surface with catalytic sites was varied to study catalyst deactivation by "talking to and between neighboring sites" (important reason of catalyst deactivating side-reaction in one-electron catalysis) [59,60]. Furthermore, the use of these dendrimer-catalytic materials under continuous reaction conditions using membrane reactors was thereafter evaluated [61].…”

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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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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“…As described in the introduction, dendrimers G 0 2 and G 1 2 were successfully employed in the Kharasch addition, with comparable activity to monomeric species. Based on these preliminary experiments, some modifications to the pincer containing dendrimers were investigated to further elucidate the factors that affect catalyst performance and to determine if these systems were amenable to membrane filtration techniques [42,43]. One of the first details addressed was the nature of the linking group between the dendrimer and the organometallic pincer species.…”

Section: Dendrimers Containing Non-ferrocene Organometallic Groups Inmentioning

confidence: 99%

Where organometallics and dendrimers merge: the incorporation of organometallic species into dendritic molecules

Chase

Gebbink

Koten

2004

Journal of Organometallic Chemistry

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This review will describe the ongoing efforts being made to incorporate organometallic fragments into the framework of dendrimers. While purely dendritic organic molecules are well known and well studied, species incorporating organometallic moieties potentially offer many benefits that are not available to only organic containing dendrimers. For example, catalytic or redox active organometallic functions can be included in the dendritic framework and impart these characteristics onto the dendrimer. This report will give an overview of the latest developments in this field by highlighting selected examples that detail novel synthetic strategies or dendrimer construction methodologies, interesting practical applications or address specific problems associated with organometallic dendrimers.

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“…1) were synthesized and their retention behaviour examined in a nanofiltration membrane reactor [10]. A filtration test (with 1) in a NFmembrane reactor (Fig.…”

Section: Homogeneous Catalysts On Dendritic Supportsmentioning

confidence: 99%

Recyclable Nanosize Homogeneous Catalysts

2004

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For industrial chemical processes, it would be highly desirable from both a commercial and an environmental point of view to incorporate the advantages of homogeneous and heterogeneous catalysis into one chemical process. The ultimate goal is to design a catalytic system with the high activity and selectivity of homogeneous catalysts, the efficient catalyst recycling of heterogeneous catalysts and which has a high (thermal) stability for extended use. Ultimately, this leads to cleaner, faster and cheaper catalytic processes and eventually will lead to green commercial processes.

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A “Dendritic Effect” in Homogeneous Catalysis with Carbosilane-Supported Arylnickel(II) Catalysts: Observation of Active-Site Proximity Effects in Atom-Transfer Radical Addition

Abstract: (5) show that 5 can be efficiently retained in a membrane reactor system. The X-ray crystal structure of the Ni(III) complex [NiCl 2 (C 6 H 2 {CH 2 NMe 2 } 2 -2,6-SiMe 3 -4)] (16), obtained from the reaction of 2 with CCl 4 , is also reported.

Cited by 214 publications

References 38 publications

Highlights of 45 years of research: A personal account

Highlights of 45 years of research: A personal account

Where organometallics and dendrimers merge: the incorporation of organometallic species into dendritic molecules

Recyclable Nanosize Homogeneous Catalysts

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