NNB-Type Tridentate Boryl Ligands Enabling a Highly Active Iridium Catalyst for C–H Borylation

Ding, Siyi; Wang, Linghua; Miao, Zongcheng; Li, Pengfei

doi:10.3390/molecules24071434

Cited by 7 publications

(7 citation statements)

References 60 publications

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“…The Shimada's group has described the preparation of iridium(III) unsaturated complexes with a PSiP pincer diphosphine, which catalyze the C−H borylation of benzene with B 2 pin 2 , whereas Driess, Hartwig and co‐workers have reported that iridium(III) precursors with bulky silylene‐aryl‐silylene pincers work for the reactions with HBpin. Recently, Li's group has used a NNB‐boryl ligand, whereas Pérez‐Torrente, Oro, and co‐workers have isolated unsaturated catalysts supported by an ONO ligand. From a mechanistic point of view, it should be noteworthy the Ozerov's studies on (POCOP)Ir systems, which have allowed them to conclude that the C−H bond activation of the arene occurs on an iridium(I) center devoid of boryl ligands (Scheme ), in contrast to the catalysts supported by neutral bidentate ligands.…”

Section: Introductionmentioning

confidence: 99%

Direct C−H Borylation of Arenes Catalyzed by Saturated Hydride‐Boryl‐Iridium‐POP Complexes: Kinetic Analysis of the Elemental Steps

Esteruelas

Martínez

Oliván

et al. 2020

Chemistry A European J

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The saturated trihydride IrH 3 {k 3-P,O,P-[xant(PiPr 2) 2 ]} (1;x ant(PiPr 2) 2 = 9,9-dimethyl-4,5-bis(diisopropylphosphino)xanthene)a ctivates the BÀHb ond of two molecules of pinacolborane (HBpin) to give H 2 ,t he hydride-boryl derivatives IrH 2 (Bpin){k 3-P,O,P-[xant(PiPr 2) 2 ]} (2)a nd IrH(Bpin) 2 {k 3-P,O,P-[xant(PiPr 2) 2 ]} (3)i nasequential manner.Complex 3 activates aC ÀHb ond of two molecules of benzene to form PhBpin and regenerates 2 and 1,a lso in as equentialm anner.T hus, complexes 1, 2,a nd 3 define two cycles for the catalytic direct CÀHb orylation of arenes with HBpin,w hich have di-hydride 2 as ac ommon intermediate. CÀHb ond activation of the arenes is the rate-determining step of both cycles, as the CÀHo xidative addition to 3 is faster than to 2.T he results from ak inetic study of the reactions of 1 and 2 with HBpin support ac ooperative function of the hydride ligands in the BÀHb ond activation.T he addition of the boron atom of the borane to ah ydride facilitates the coordinationo ft he BÀHb ond through the formation of k 1-a nd k 2-dihydrideborate intermediates. Scheme1.Proposed catalytic cycle for the borylation of arenes catalyzed by Ir(Bpin) 3 L 2 .

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Section: Introductionmentioning

confidence: 99%

Direct C−H Borylation of Arenes Catalyzed by Saturated Hydride‐Boryl‐Iridium‐POP Complexes: Kinetic Analysis of the Elemental Steps

Esteruelas

Martínez

Oliván

et al. 2020

Chemistry A European J

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“…The fac ‐tridentate ligand worked as an efficient ligand for the reaction and utilized both boron atoms in the diboron reagent. We envisioned that LLX‐type mer ‐tridentate ligands which generated thermally stable iridium‐complex would be suitable for this reaction (Scheme 1C) [14, 15] . Herein, we report the iridium‐catalyzed C(sp 3 )−H borylation using bipyridine‐based NNSi ligands.…”

Section: Methodsmentioning

confidence: 99%

Iridium‐Catalyzed C(sp³)−H Borylation Using Silyl‐Bipyridine Pincer Ligands

2022

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New ligands for the iridium-catalyzed C-(sp 3 )À H borylation of aliphatic compounds were established. In sharp contrast to 6-methyl-2,2'-bipyridine and 6-isobutyl-2,2'-bipyridine, 2,2'-bipyridine and 1,10-phenanthroline derivatives bearing a hydrosilylmethyl group (which would give a thermally stable NNSi pincer complex) served as suitable ligands for the reaction. Among them, a phenanthroline-based NNSi pincer ligand was shown to be an excellent ligand, and various aliphatic compounds were efficiently converted to the corresponding borylated products using the Ir/NNSi pincer catalyst system. The NNSi pincer ligand showed unique selectivity and enabled the iridium-catalyzed C(sp 3 )À H borylation using pinacolborane [HÀ B(pin)] instead of B 2 (pin) 2 . The formation of an iridium complex bearing a quinoline-based NNSi pincer ligand from [IrCl(cod)] 2 was observed, and the catalytic activity of the complex was demonstrated.

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“…Several isomeric amino-substituted 2,2′-bipyridines were reported as fluorescent indicators for Zn (II) and fluorescent dyes for the imaging of prostate cells [ 14 ]. Finally, arylamino-2,2′-bipyridines were reported as convenient synthons for the construction of various fused polynuclear systems [ 15 , 16 , 17 ].…”

Section: Introductionmentioning

confidence: 99%

Synthesis and Photophysical Properties of α-(N-Biphenyl)-Substituted 2,2′-Bipyridine-Based Push–Pull Fluorophores

et al. 2022

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A series of new α-(N-biphenyl)-substituted 2,2′-bipyridines were obtained through the combination of the ipso-nucleophilic aromatic substitution of the C5-cyano group, aza-Diels–Alder and Suzuki cross-coupling reactions, starting from 5-cyano-1,2,4-triazines. For the obtained compounds, photophysical and fluorosolvatochromic properties were studied. Fluorophores 3l and 3b demonstrated unexpected AIEE activity, while 3a and 3h showed promising nitroexplosive detection abilities.

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NNB-Type Tridentate Boryl Ligands Enabling a Highly Active Iridium Catalyst for C–H Borylation

Cited by 7 publications

References 60 publications

Direct C−H Borylation of Arenes Catalyzed by Saturated Hydride‐Boryl‐Iridium‐POP Complexes: Kinetic Analysis of the Elemental Steps

Direct C−H Borylation of Arenes Catalyzed by Saturated Hydride‐Boryl‐Iridium‐POP Complexes: Kinetic Analysis of the Elemental Steps

Iridium‐Catalyzed C(sp³)−H Borylation Using Silyl‐Bipyridine Pincer Ligands

Synthesis and Photophysical Properties of α-(N-Biphenyl)-Substituted 2,2′-Bipyridine-Based Push–Pull Fluorophores

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NNB-Type Tridentate Boryl Ligands Enabling a Highly Active Iridium Catalyst for C–H Borylation

Cited by 7 publications

References 60 publications

Direct C−H Borylation of Arenes Catalyzed by Saturated Hydride‐Boryl‐Iridium‐POP Complexes: Kinetic Analysis of the Elemental Steps

Direct C−H Borylation of Arenes Catalyzed by Saturated Hydride‐Boryl‐Iridium‐POP Complexes: Kinetic Analysis of the Elemental Steps

Iridium‐Catalyzed C(sp3)−H Borylation Using Silyl‐Bipyridine Pincer Ligands

Synthesis and Photophysical Properties of α-(N-Biphenyl)-Substituted 2,2′-Bipyridine-Based Push–Pull Fluorophores

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Iridium‐Catalyzed C(sp³)−H Borylation Using Silyl‐Bipyridine Pincer Ligands