Modern Organometallic Multidentate Ligand Design Strategies: The Birth of the Privileged “Pincer” Ligand Platform

Chase, Preston A.; Gossage, Robert A.; Koten, Gerard van

doi:10.1007/3418_2015_131

Cited by 24 publications

(22 citation statements)

References 48 publications

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“…Moreover, compounds featuring 2e-3c bonding of C ipso -anion were encountered in NCN-pincer lithium and cuprate chemistry but also in NCN-pincer tantalum-zinc bimetallic compounds [43]. Finally, the binding of [MX n L m ]-cations in the h 5 -mode to the arene system of arylpincer metal species was realized which likewise lead to bimetallic pincer complexes [44] (see Fig. 14).…”

Section: Ncn-(and Some Xcx-) Pincer Chemistry: Fundamentals Catalysimentioning

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: Ncn-(and Some Xcx-) Pincer Chemistry: Fundamentals Catalysimentioning

confidence: 99%

Highlights of 45 years of research: A personal account

Koten

2017

Journal of Organometallic Chemistry

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“…These possibilities demonstrate the synthetic versatility of AAD and the very high flexibility, selectivity, and activity of pincer catalysts. These complexes might even be considered a privileged family of catalysts [262][263][264][265][266].…”

Section: Figurementioning

confidence: 99%

Recent Progress with Pincer Transition Metal Catalysts for Sustainability

2020

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Our planet urgently needs sustainable solutions to alleviate the anthropogenic global warming and climate change. Homogeneous catalysis has the potential to play a fundamental role in this process, providing novel, efficient, and at the same time eco-friendly routes for both chemicals and energy production. In particular, pincer-type ligation shows promising properties in terms of long-term stability and selectivity, as well as allowing for mild reaction conditions and low catalyst loading. Indeed, pincer complexes have been applied to a plethora of sustainable chemical processes, such as hydrogen release, CO2 capture and conversion, N2 fixation, and biomass valorization for the synthesis of high-value chemicals and fuels. In this work, we show the main advances of the last five years in the use of pincer transition metal complexes in key catalytic processes aiming for a more sustainable chemical and energy production.

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“…The very interesting class of metal “pincer” complexes had its origins in the mid‐1970s, predominantly through the efforts of the Shaw, van Koten, and Kaska groups, and it is likely that over a thousand such compounds are known , . In these species, bidentate coordination typically involving lone pairs of meta ‐phenyl‐tethered pairs of phosphines, amines, ethers, or thioethers leads to the metal center being in such close proximity to the intervening phenyl carbon atom and its substituent that oxidative addition across that bond is quite common , …”

Section: “Pincer Complexes”mentioning

confidence: 99%

Transition‐Metal Complexes with (C–C)→M Agostic Interactions

Harvey

Ernst

2017

Eur J Inorg Chem

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The coordination of sigma bonding electron density to a Lewis acid was for some time largely the domain of boron hydride chemistry. Subsequently it was found that C-H bonds could undergo intramolecular coordination to metal centers, forming what are now known as "agostic bonds" and "agostic complexes". Thereafter, even the H-H bond in molecular hydrogen was found to be capable of coordination, leading to what are commonly referred to as "sigma complexes". Eventually, coordination by much more shielded C-C bonds was estab-[a] US Navy, Naval inorganic chemistry from the University of Utah in 2005, studying with Professor Richard D. Ernst. His graduate studies were focused on the synthesis and characterization of early-transition-metal organometallic cage structures and metallacyclobutanes. Many of the compounds studied in his research exhibited unique C-C agostic bonding interactions. His current areas of interest include catalysis, advanced biofuels, high-temperature thermosetting resins, and green chemistry. Richard D. Ernst is a Professor of Chemistry at the University of Utah. He received his B.S. degree in chemistry from the University of California in Berkeley in 1973 and his Ph.D. degree in inorganic chemistry from Northwestern University in 1977. His major areas of interest include organometallic chemistry, particularly of metal-pentadienyl compounds, coordination chemistry, and catalysis of the Fischer-Tropsch and Water Gas Shift reactions.

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Modern Organometallic Multidentate Ligand Design Strategies: The Birth of the Privileged “Pincer” Ligand Platform

Cited by 24 publications

References 48 publications

Highlights of 45 years of research: A personal account

Highlights of 45 years of research: A personal account

Recent Progress with Pincer Transition Metal Catalysts for Sustainability

Transition‐Metal Complexes with (C–C)→M Agostic Interactions

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