Redox-Active Pincer Ligands

Vlugt, Jarl Ivar van der

doi:10.1007/3418_2020_68

Cited by 9 publications

(12 citation statements)

References 212 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…In the case of first-row transition metals, they can enforce two electron redox processes, suppressing the otherwise favorable single-electron-transfer reactions. This feature enables them to emulate the catalytic activity of their heavier congeners . Among these ligands, pyridinediimines (PDI) have been proven to be privileged scaffolds, especially in iron catalysis. , Recently, our group has demonstrated that introducing additional nitrogen atoms into the supporting heterocyclic ring can significantly change the reactivity of such systems .…”

Section: Introductionmentioning

confidence: 99%

Redox Activity of Iron Diazine-Diimine Carbonyl and Dinitrogen Complexes: A Comparative Study of the Influence of the Heterocyclic Ring

et al. 2021

View full text Add to dashboard Cite

A detailed investigation of the electronic structure of diazinediimine iron complexes and their comparison with the pyridine analogues reveals subtle but important differences, imparted by the supporting heterocycle. In the case of LFe(CO)2 complexes (L = pyrazine- and pyrimidinediimine), the characterization of three available redox states confirmed that whereas the nature of the electron-transfer processes is similar, the differences in π-acidity of the supporting heterocycle significantly affect the redox potentials. The reduction of LFe(CO)2 can yield either a ligand-centered radical (for L = pyrimidine) or a C–C-bonded dimer (for L = pyrazine), supported by a dearomatized core. In the latter case, the C–C bond can be reversibly cleaved oxidatively. Compared to the carbonyl analogues, employing weak-field N2 ligands triggers changes in electronic structure for the neutral and reduced LFe(N2) complexes (L = pyrimidinediimine). En route to the synthesis of the nitrogen complexes, the square-planar LFeCl (L = pyrimidinediimine) was isolated. The monoradical character of the supporting chelate triggers the asymmetric distribution of electron density around the heterocycle.

show abstract

Section: Introductionmentioning

confidence: 99%

Redox Activity of Iron Diazine-Diimine Carbonyl and Dinitrogen Complexes: A Comparative Study of the Influence of the Heterocyclic Ring

et al. 2021

View full text Add to dashboard Cite

show abstract

“…Yield near quantitative. 1 H NMR (300 MHz, DMSO-d 6 , d, ppm): 7.53 (m, 4H), 7.12 (m, 4H), 7.00 (s, 4H). 13 Complex 3.…”

Section: Synthesis Of 1-3mentioning

confidence: 99%

“…Each CV curve and UV-vis spectrum were reproduced at least three times. 1 H NMR (300 MHz) and 13 C NMR (75 MHz) were recorded in DMSO-d 6 on Bruker AM300 at ambient temperature. NMR spectra were referenced using residual DMSO-d 6 ( 1 H NMR d ¼ 2.5 ppm, 13 C NMR d ¼ 39.5 ppm).…”

Section: Instrumentationmentioning

confidence: 99%

“…The use of redox-active ligands is an effective approach to control and regulate the electrochemical, photochemical and magnetic properties of organometallic compounds, to manipulate their reactivity in chemical processes. [1][2][3][4][5] In this regard, the concept of redox-active ligands has found various applications in the production of new materials with useful properties 6 and catalysis 7,8 as well as chemistry of organogermanium derivatives 9-12 etc. Germanium is a "special" element of the Periodic Table . Its chemical properties are similar to ones of the ancestor of the 14th groupcarbonthe basic element of organic chemistry.…”

Section: Introductionmentioning

confidence: 99%

See 1 more Smart Citation

Supramolecular D⋯A-layered structures based on germanium complexes with 2,3-dihydroxynaphthalene and N,N′-bidentate ligands

et al. 2021

View full text Add to dashboard Cite

show abstract

“…Pincer complexes of transition metals have attracted a great deal of attention as they have been used in a myriad of organic transformations . Because of their unique design, their high thermal stability, and the meridional tridentate nature of pincer ligands, they are privileged platforms for stabilization of metal complexes with usually enhanced catalytic performances compared to those of monodentate ligands …”

Section: Introductionmentioning

confidence: 99%

Palladium(II) Complexes of a Neutral CCC-Tris(N-heterocyclic carbene) Pincer Ligand: Synthesis and Catalytic Applications

et al. 2021

View full text Add to dashboard Cite

Treatment of tris-azolium precursor 1 with palladium acetate under thermal conditions provided a CCC-pincer palladium(II) complex (2) bearing three NHCs (one imidazolylidene and two triazolylidenes) and one iodide ligand. Further treatment of complex 2 with an excess of AgSbF6 generates tris(carbene) dicationic palladium complex 3 in which the iodine ligands are exchanged with SbF6 anions and the metal center is stabilized by one acetonitrile ligand. Complexes 2 and 3 were tested in several cross coupling reactions showing high conversions under low catalyst loadings and mild reaction conditions. Additionally, complexes 2 and 3 performed well in the hydrosilylation of terminal alkynes with good selectivity toward the E-isomer.

show abstract

Redox-Active Pincer Ligands

Cited by 9 publications

References 212 publications

Redox Activity of Iron Diazine-Diimine Carbonyl and Dinitrogen Complexes: A Comparative Study of the Influence of the Heterocyclic Ring

Redox Activity of Iron Diazine-Diimine Carbonyl and Dinitrogen Complexes: A Comparative Study of the Influence of the Heterocyclic Ring

Supramolecular D⋯A-layered structures based on germanium complexes with 2,3-dihydroxynaphthalene and N,N′-bidentate ligands

Palladium(II) Complexes of a Neutral CCC-Tris(N-heterocyclic carbene) Pincer Ligand: Synthesis and Catalytic Applications

Contact Info

Product

Resources

About