Chelating cyclic aminomethylphosphines and their transition metal complexes as a promising basis of bioinspired mimetic catalysts

Карасик, А. А.; Balueva, A. S.; Musina, Elvira I.; Sinyashin, Оleg G.

doi:10.1016/j.mencom.2013.09.001

Cited by 37 publications

(16 citation statements)

References 67 publications

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“…[16][17][18][23][24][25] Moreover, luminescence of Au(I) phosphine complexes can also be tuned by any non-covalent interactions with metal centers and constituting ligands, which can affect the charge distribution or induce conformational changes within the complexes. 18 The previously documented synthetic strategy 26,27 enables us to get series of cyclic diphosphine ligands with different nature of substituting groups in order to vary electron donating or accepting capacity of the ligands. Recently published work reports synthesis and vapochromism of a binuclear phosphinechloride Au(I) complex with a cyclic diphosphine PNNP ligand ((AuCl) 2 L in Scheme 1).…”

Section: Introductionmentioning

confidence: 99%

“Host–guest” binding of a luminescent dinuclear Au(i) complex based on cyclic diphosphine with organic substrates as a reason for luminescence tuneability

et al. 2016

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Section: Introductionmentioning

confidence: 99%

“Host–guest” binding of a luminescent dinuclear Au(i) complex based on cyclic diphosphine with organic substrates as a reason for luminescence tuneability

et al. 2016

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“…88.6(3) F1-Fe1-P7 95.9(2) N43-Fe1- Both diazadiphosphacyclooctane ligands (N(1)P(3)N(5)P (7) and N(1B)P(3B)N(5B)P(7B)) had chair-boat conformations, so the substituents on nitrogen atoms in the chair and boat parts of the heterocycles were in an essentially different environment. That explained the nonequivalence of these substituents in NMR spectra.…”

Section: Resultsmentioning

confidence: 99%

Synthesis and Structure of Iron (II) Complexes of Functionalized 1,5-Diaza-3,7-Diphosphacyclooctanes

et al. 2020

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In order to synthesize new iron (II) complexes of 1,5-diaza-3,7-diphosphacyclooctanes with a wider variety of the substituents on ligands heteroatoms (including functionalized ones, namely, pyridyl groups) and co-ligands, it was found that these ligands with relatively small phenyl, benzyl, and pyridin-2-yl substituents on phosphorus atoms in acetonitrile formed bis-P,P-chelate cis-complexes [L2Fe(CH3CN)2]2+ (BF4)2−, whereas P-mesityl-substituted ligand formed only monoligand P,P-complex [LFe(CH3CN)4]2+ (BF4)2−. 3,7-dibenzyl-1,5-di(1′-(R)-phenylethyl)-1,5-diaza-3,7-diphosphacyclooctane reacted with hexahydrate of iron (II) tetrafluoroborate in acetone to give an unusual bis-ligand cationic complex of the composition [L2Fe(BF4)]+ BF4−, where two fluorine atoms of the tetrafluoroborate unit occupied two pseudo-equatorial positions at roughly octahedral iron ion, according to X-ray diffraction data. 1,5-diaza-3,7-diphosphacyclooctanes replaced tetrahydrofurane and one of the carbonyl ligands of cyclopentadienyldicarbonyl(tetrahydrofuran)iron (II) tetrafluoroborate to form heteroligand complexes [CpFeL(CO)]+BF4−. The structural studies in the solid phase and in solutions showed that diazadiphosphacyclooctane ligands of all complexes adopted chair-boat conformations so that their nitrogen atoms were in close proximity to the central iron ion. The redox properties of the obtained complexes were performed by the cyclic voltammetry method.

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“…In contrast with 11 – 13 , 14 cannot accommodate a transition metal ion in a trans configuration because of the smaller ring and hence forms C 2 ‐ twist complexes of Zr(IV), Hf(IV), Y(III), and the lanthanides . Even smaller N 2 P 2 macrocycles tend to act as P,P‐bidentate ligands, that is as diphosphines …”

Section: General Considerations and Early Resultsmentioning

confidence: 99%

Iron Complexes with Chiral N/P Macrocycles as Catalysts for Asymmetric Transfer Hydrogenation

Mezzetti

2017

Israel Journal of Chemistry

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The present account describes the development of chiral, C 2 -symmetric N/P macrocyclic ligands that attune to the size and electronic properties of the iron(II) ion to give robust complexes under catalysis conditions. This is not trivial, as the complexes of base metals are substantially less stable than those of precious metals. Also, as these N 2 P 2 macrocycles feature stereogenic P atoms, the control of the stereochemistry at phosphorus is a key synthetic issue. Still, as the macrocyclic effect was insufficient to give robust catalysts under hydrogen transfer conditions, we had to dig deeper into the toolbox of coordination chemistry and use strong-field ancillary ligands other than CO, specifically isonitriles, which additionally offer a further handle to tune the catalyst. The reward was the discovery of the first iron(II) catalyst for the asymmetric transfer hydrogenation of polar double bonds that is highly enantioselective for a broad scope of substrates.

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Chelating cyclic aminomethylphosphines and their transition metal complexes as a promising basis of bioinspired mimetic catalysts

Cited by 37 publications

References 67 publications

“Host–guest” binding of a luminescent dinuclear Au(i) complex based on cyclic diphosphine with organic substrates as a reason for luminescence tuneability

“Host–guest” binding of a luminescent dinuclear Au(i) complex based on cyclic diphosphine with organic substrates as a reason for luminescence tuneability

Synthesis and Structure of Iron (II) Complexes of Functionalized 1,5-Diaza-3,7-Diphosphacyclooctanes

Iron Complexes with Chiral N/P Macrocycles as Catalysts for Asymmetric Transfer Hydrogenation

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