Hydrogenation of a Rhodium Peroxido Complex by Formate Derivatives: Mechanistic Studies and the Catalytic Formation of H2O2 from O2

Meier, Gregor; Braun, Thomas

doi:10.1002/anie.201207073

Cited by 30 publications

(22 citation statements)

References 142 publications

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“…Treatment of late transition‐metal complexes with dioxygen often give peroxido complexes, which can act as key intermediates in the conversion of organic compounds 1k. 2 At rhodium, the oxygen atoms of the peroxido ligand are often nucleophilic 2a,c. 3 Thus, a reaction of trans ‐[Rh(O 2 )(4‐C 5 NF 4 )(CN t Bu)(PEt 3 ) 2 ] ( 1 a ) with formic acid yields initially the rhodium hydroperoxido complex trans ‐[Rh(OOH){OC(O)H}(4‐C 5 NF 4 )(CN t Bu)(PEt 3 ) 2 ] at low temperatures 2c.…”

Section: Methodsmentioning

confidence: 99%

“…2 At rhodium, the oxygen atoms of the peroxido ligand are often nucleophilic 2a,c. 3 Thus, a reaction of trans ‐[Rh(O 2 )(4‐C 5 NF 4 )(CN t Bu)(PEt 3 ) 2 ] ( 1 a ) with formic acid yields initially the rhodium hydroperoxido complex trans ‐[Rh(OOH){OC(O)H}(4‐C 5 NF 4 )(CN t Bu)(PEt 3 ) 2 ] at low temperatures 2c. Subsequently, hydrogen peroxide and the rhodium(I) complex trans ‐[Rh(4‐C 5 NF 4 )(CN t Bu)(PEt 3 ) 2 ] ( 2 ) are furnished.…”

Section: Methodsmentioning

confidence: 99%

“…3 a is stable in solution at room temperature, but decomposes under vacuum immediately due to the loss of the pyridine ligand. Note that trans ‐[Rh(O 2 )(4‐C 5 NF 4 )(CN t Bu)(PEt 3 ) 2 ] ( 1 a ) reacts with HCl or HCOOH in a comparable manner to give the hydroperoxido complexes trans ‐[Rh(OOH){X}(4‐C 5 NF 4 )(CN t Bu)(PEt 3 ) 2 ] (X=Cl, OC(O)H), but the complexes are only stable at temperatures below −50 °C 2a,c…”

Section: Methodsmentioning

confidence: 99%

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Rhodium‐Mediated Oxygenation of Nitriles with Dioxygen: Isolation of Rhodium Derivatives of Peroxyimidic Acids

Bittner

Braun

Herrmann

et al. 2015

Chemistry A European J

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Dioxygen is used as the oxygenation agent in the rhodium-mediated conversion of nitriles into amides. The characterization of intermediate species and model compounds as well as isotope-labeling studies provided an insight into the reaction mechanism. The conversions of rhodium hydroperoxido or methylperoxido complexes with nitriles into metallacyclic rhodium-κ(2)-(N,O)-peroxyimidate compounds represent essential key steps. The former are accessible from a rhodium(III) peroxido complex and the latter represent rhodium derivatives of Payne's reagent (peroxyimidic acids).

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Section: Methodsmentioning

confidence: 99%

Section: Methodsmentioning

confidence: 99%

Section: Methodsmentioning

confidence: 99%

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Rhodium‐Mediated Oxygenation of Nitriles with Dioxygen: Isolation of Rhodium Derivatives of Peroxyimidic Acids

Bittner

Braun

Herrmann

et al. 2015

Chemistry A European J

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“…Noteworthy is that complex 2 is one of the few examples of a s-bound trifluoropropynyl ligand at ac omplexo fatransition metal. The 31 P{ 1 H} NMR spectruma t1 21.5 MHz discloses a system of higher order that simplifies at 242.8 MHz (see the Supporting Information), although it still represents aspectrum of highero rder.T oo btain the coupling constants, the spectrum of 2 was simulated [15] (Figure 1) to be an A 2 BMX 3 spin system.T wo resonances in a1:2 ratio at d = 20.5 and 19.1 ppm are observed that have rhodium-phosphorus coupling constants typical for rhodium(I) complexes( J = 128.9 and1 34.8 Hz, respectively), [16] and the coupling constantb etween the phosphorusn uclei is J = 39.4 Hz. [14a-f] Complex 2 shows am olecular ion peak at m/z = 550 by liquid injection field desorption/ionizationm asss pectrometry (LIFDI-MS).…”

Section: Resultsmentioning

confidence: 99%

Reactivity of 3,3,3‐Trifluoropropyne at Rhodium Complexes: Development of Hydroboration Reactions

Hahmann

Talavera

et al. 2018

Chemistry A European J

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The rhodium compounds [Rh(C≡CCF )(PEt ) ] (2), fac-[RhH(C≡CCF ) (PEt ) ] (3), and fac-[Rh{(E)-CH=CHCF }(C≡CCF ) (PEt ) ] (4) were synthesized by reactions of the rhodium(I) complexes [Rh(H)(PEt ) ] (1) and [Rh(Bpin)(PEt ) ] (5, HBpin=pinacolborane) with the alkyne 3,3,3-trifluoropropyne. Reactivity studies of [Rh(C≡CCF )(PEt ) ] (2) were performed with CO and CO to form [Rh(C≡CCF )(CO)(PEt ) ] (7) and subsequently trans-[Rh(C≡CCF )(CO)(PEt ) ] (8) as well as the labeled derivatives. Using 1-4 as catalysts, hydroboration reactions selectively afforded borylated building blocks.

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“…The crystallographic data and spectral features of 4 are consistent with those of related Rh III (η 2 -O 2 ) complexes. 5,34,39,40 The X-ray crystal structure of 4b, which is provided in Figure 3 Inorg. Chem.…”

Section: ■ Resultsmentioning

confidence: 99%

Oxygen Reduction Mechanism of Monometallic Rhodium Hydride Complexes

2015

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The reduction of O2 to H2O mediated by a series of electronically varied rhodium hydride complexes of the form cis,trans-Rh(III)Cl2H(CNAd)(P(4-X-C6H4)3)2 (2) (CNAd = 1-adamantylisocyanide; X = F (2a), Cl (2b), Me (2c), OMe (2d)) was examined through synthetic and kinetic studies. Rhodium(III) hydride 2 reacts with O2 to afford H2O with concomitant generation of trans-Rh(III)Cl3(CNAd)(P(4-X-C6H4)3)2 (3). Kinetic studies of the reaction of the hydride complex 2 with O2 in the presence of HCl revealed a two-term rate law consistent with an HX reductive elimination (HXRE) mechanism, where O2 binds to a rhodium(I) metal center and generates an η(2)-peroxo complex intermediate, trans-Rh(III)Cl(CNAd)(η(2)-O2)(P(4-X-C6H4)3)2 (4), and a hydrogen-atom abstraction (HAA) mechanism, which entails the direct reaction of O2 with the hydride. Experimental data reveal that the rate of reduction of O2 to H2O is enhanced by electron-withdrawing phosphine ligands. Complex 4 was independently prepared by the addition of O2 to trans-Rh(I)Cl(CNAd)(P(4-X-C6H4)3)2 (1). The reactivity of 4 toward HCl reveals that such peroxo complexes are plausible intermediates in the reduction of O2 to H2O. These results show that the given series of electronically varied rhodium(III) hydride complexes facilitate the reduction of O2 to H2O according to a two-term rate law comprising HXRE and HAA pathways and that the relative rates of these two pathways, which can occur simultaneously and competitively, can be systematically modulated by variation of the electronic properties of the ancillary ligand set.

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Hydrogenation of a Rhodium Peroxido Complex by Formate Derivatives: Mechanistic Studies and the Catalytic Formation of H₂O₂ from O₂

Cited by 30 publications

References 142 publications

Rhodium‐Mediated Oxygenation of Nitriles with Dioxygen: Isolation of Rhodium Derivatives of Peroxyimidic Acids

Rhodium‐Mediated Oxygenation of Nitriles with Dioxygen: Isolation of Rhodium Derivatives of Peroxyimidic Acids

Reactivity of 3,3,3‐Trifluoropropyne at Rhodium Complexes: Development of Hydroboration Reactions

Oxygen Reduction Mechanism of Monometallic Rhodium Hydride Complexes

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