Diaminoarylnickel(II) “Pincer” Complexes:  Mechanistic Considerations in the Kharasch Addition Reaction, Controlled Polymerization, and Dendrimeric Transition Metal Catalysts

Koten, Gerard van; Gossage, Robert A.; Kuil, van de L.A.

doi:10.1021/ar970221i

Cited by 377 publications

(190 citation statements)

References 104 publications

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“…This renders the catalyst amenable to nanofiltration separation techniques [49,50]. The catalysts studied in this regard are complexes of the well-known "pincer" ligand system [51][52][53][54][55][56]. Dendritic supports offer many advantages in this area but, due to their flexible nature, are not retained by nanofiltration membranes to the same extent as rigid molecules of similar (or lesser) molecular weight.…”

Section: Introductionmentioning

confidence: 99%

Ring closing metathesis employing organometallic substrates and the templated synthesis of macrocycles

Chase

Lutz

Spek

et al. 2006

Journal of Molecular Catalysis A: Chemical

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Templation is a well-known strategy for the selective generation of complex products. Ring-closing metathesis, catalyzed by well-characterized Ru and Mo catalysts, is a powerful method for C C bond formation and has certainly developed into one of the most important modern reactions in organic synthesis and in polymer chemistry. Despite the extensive research on this reaction, the use of organometallic containing substrates is not well-studied. Here, we give a detailed account of our ongoing efforts to employ ring-closing metathesis with bis(␣-olefin) substituted pyridines in the presence of trimeric metallopincer templates for the selective synthesis of macroheterocycles with ring sizes up to 81 atoms.

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Section: Introductionmentioning

confidence: 99%

Ring closing metathesis employing organometallic substrates and the templated synthesis of macrocycles

Chase

Lutz

Spek

et al. 2006

Journal of Molecular Catalysis A: Chemical

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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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“…In this regard, we have extensively studied NCN-pincer metal complexes of the nickel triad (Ni, Pd, Pt). NCN-Z nickel(II) complexes, e.g., show a remarkable relation between the Ni(II)/Ni(III) oxidation potential and the electronic nature of para-substituent Z [3]. A linear Hammett relationship was established between the σ p -Hammett substituent constant and the oxidation potential, which translated itself consequently to the overall catalytic reactivity of the complexes in the redox-based Karasch-addition of CCl 4 to methyl metacrylate.…”

Section: Introductionmentioning

confidence: 95%

“…Our interest is focused on the parafunctionalization of NCN-pincer metal complexes (NCN = 2,6-bis[(dimethylamino)methyl]phenyl anion) [1][2][3][4][5] with a wide variety of different substituents and anchoring points. Variation of the para-substituent Z in NCN-Z metal complexes can be exploited to fine-tune the electronic, catalytic, spectroscopic, and diagnostic properties of the complexes and can furthermore be used to advantage in a synthetic sense for the further modification of pincer complexes.…”

Section: Introductionmentioning

confidence: 99%

NCN–pincer palladium complexes with multiple anchoring points for functional groups

Slagt

Zwieten

Moerkerk

et al. 2004

Coordination Chemistry Reviews

101

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Diaminoarylnickel(II) “Pincer” Complexes: Mechanistic Considerations in the Kharasch Addition Reaction, Controlled Polymerization, and Dendrimeric Transition Metal Catalysts

Cited by 377 publications

References 104 publications

Ring closing metathesis employing organometallic substrates and the templated synthesis of macrocycles

Ring closing metathesis employing organometallic substrates and the templated synthesis of macrocycles

Highlights of 45 years of research: A personal account

NCN–pincer palladium complexes with multiple anchoring points for functional groups

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