Organometallic Pincer Chemistry

Koten, Gerard van; Milstein, David; Castonguay, Annie

doi:10.1007/978-3-642-31081-2

Cited by 204 publications

(3 citation statements)

References 8 publications

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“…This controlled release is facilitated by a high TM barrier (as in the case of the N'CN pincer palladacycles) or by a highly endergonic reaction energy (as in the case of the PCN pincer palladacycles). Facile formation of Pd(0) can lead to the formation of inactive palladium black [66]. The agglomeration of palladium nano-particles to form catalytically inactive palladium black is a key catalyst deactivation route [67,68].…”

Section: Effect Of Substituents On the Catalytic Activity Of The Novementioning

confidence: 99%

Rationalization of the mechanism of in situ Pd(0) formation for cross-coupling reactions from novel unsymmetrical pincer palladacycles using DFT calculations

Boonseng

Roffe

Targema

et al. 2017

Journal of Organometallic Chemistry

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Section: Effect Of Substituents On the Catalytic Activity Of The Novementioning

confidence: 99%

Rationalization of the mechanism of in situ Pd(0) formation for cross-coupling reactions from novel unsymmetrical pincer palladacycles using DFT calculations

Boonseng

Roffe

Targema

et al. 2017

Journal of Organometallic Chemistry

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“…Within the project devoted to pincer complexes having a specific tridentate monoanionic framework, the importance of which expands from catalytic applications to materials science, ,, recently we have shown that functionalized carboxamides with ancillary donor groups both in the amine and acid parts can act as pincer-type ligands upon coordination with the Pd(II) ions . The resulting N-metalated palladocycles proved to be efficient and readily tunable catalysts for the Suzuki cross-coupling.…”

Section: Introductionmentioning

confidence: 99%

Highly Cytotoxic Palladium(II) Pincer Complexes Based on Picolinylamides Functionalized with Amino Acids Bearing Ancillary S-Donor Groups

et al. 2017

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The reactions of picolinyl and 4-chloropicolinyl chlorides with methyl esters of S-methyl-l-cysteine, l- and d-methionine, and l-histidine afforded a series of functionalized carboxamides, which readily formed pincer-type complexes upon interaction with PdCl(NCPh) in solution under mild conditions. The direct cyclopalladation of the ligands derived was also accomplished in the solid phase, in particular, mechanochemically, although it was complicated by the partial deactivation of the starting amides. The resulting complexes with 5,5- and 5,6-membered fused metallocycles were fully characterized by IR and NMR spectroscopy, including variable-temperature and 2D-NMR studies. In the case of some cysteine- and methionine-based derivatives, the realization of κ-N,N,S-coordination was supported by X-ray diffraction. The cytotoxic effects of these complexes were examined on HCT116, MCF7, and PC3 human cancer cell lines as well as HEK293 as a representative of normal cells. The comparative studies allowed us to determine that the presence of the sulfide ancillary donor group is crucial for cytotoxic activity of this type of Pd(II) complexes. The main structure-activity relationships and the most promising palladocycles were outlined. The additional studies by gel electrophoresis revealed that 4-chloropicolinyl derivatives, despite the nature of an amino acid, can bind with DNA and inhibit topoisomerase I activity.

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“…This rigid arrangement confers a high stability to the complex, which is further stabilized by the substituents on the donor atoms creating a hydrophobic pocket surrounding the metal ion. Classic pincers are those able to form cyclometalated complexes [71] such as the ECE (e.g., PCP, NCN, SCS, and PCN) [72] type, but PNN, PNO, PNP, and NNN compounds have also been proposed for catalytic purposes, such as the PNN ligand forming the so-called Milstein's catalyst with ruthenium [73]. PCPs have probably been the most studied class of pincer ligands and extensively applied in catalysis, even with their P-chiral derivatives [74], but many other species have also gathered good success in this field due to their versatility and propensity to modification or derivatization, for a better tuning of the complex properties.…”

Section: Pincer Ligandsmentioning

confidence: 99%

Rh(I) Complexes in Catalysis: A Five-Year Trend

et al. 2021

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Rhodium is one of the most used metals in catalysis both in laboratory reactions and industrial processes. Despite the extensive exploration on “classical” ligands carried out during the past decades in the field of rhodium-catalyzed reactions, such as phosphines, and other common types of ligands including N-heterocyclic carbenes, ferrocenes, cyclopentadienyl anion and pentamethylcyclopentadienyl derivatives, etc., there is still lively research activity on this topic, with considerable efforts being made toward the synthesis of new preformed rhodium catalysts that can be both efficient and selective. Although the “golden age” of homogeneous catalysis might seem over, there is still plenty of room for improvement, especially from the point of view of a more sustainable chemistry. In this review, temporally restricted to the analysis of literature during the past five years (2015–2020), the latest findings and trends in the synthesis and applications of Rh(I) complexes to catalysis will be presented. From the analysis of the most recent literature, it seems clear that rhodium-catalyzed processes still represent a stimulating challenge for the metalloorganic chemist that is far from being over.

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Organometallic Pincer Chemistry

Cited by 204 publications

References 8 publications

Rationalization of the mechanism of in situ Pd(0) formation for cross-coupling reactions from novel unsymmetrical pincer palladacycles using DFT calculations

Rationalization of the mechanism of in situ Pd(0) formation for cross-coupling reactions from novel unsymmetrical pincer palladacycles using DFT calculations

Highly Cytotoxic Palladium(II) Pincer Complexes Based on Picolinylamides Functionalized with Amino Acids Bearing Ancillary S-Donor Groups

Rh(I) Complexes in Catalysis: A Five-Year Trend

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