Does an Axial Propeller Shape on a Dirhodium(III,III) Core Affect Equatorial Ligand Chirality?

Doyle, Michael P.; Shabashov, Dmitry; Zhou, Lei; Zavalij, Peter Y.; Welch, Christopher J.; Pirzada, Zainab

doi:10.1021/om2003078

Cited by 9 publications

(5 citation statements)

References 21 publications

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“…This coordination mode of acetate with dirhodium(II) complexes has been observed by Gois and Li. , Luckily, an independent reaction of Rh 2 (OAc) 4 (1.0 equiv) and L6 (1.0 equiv) in the absence of aryl boronic acid and diketone in toluene at 80 °C gave C–H metallic rhodium complex M6 (Figure B), which is collateral evidence of the above coordination mode. The formation of dirhodium-aryl species, i.e., M4 , via transmetalation of M3 with arylboronic acid had been previously studied by Doyle and co-workers . Transmetalation is considered as the rate-determining step, which is consistent with the kinetic behaviors observed in Figure d–f.…”

Section: Resultssupporting

confidence: 78%

“…The formation of dirhodium-aryl species, i.e., M4, via transmetalation of M3 with arylboronic acid had been previously studied by Doyle and co-workers. 12 Transmetalation is considered as the rate-determining step, which is consistent with the kinetic behaviors observed in Figure 3d−f. Subsequently, stereoselective carbonyl addition delivered the oxyrhodium M5.…”

Section: ■ Introductionsupporting

confidence: 78%

“…In 2001, Fürstner and Krause first proved that IMes, the axial ligand of the dirhodium(II) complex, enabled the dirhodium(II) complexes to show new catalytic activity: the arylations of aldehydes with boronic acids . In the next two decades, the strategy of adjusting the axial ligands was proven to be a valuable way to tune the reactivities of dirhodium(II) complexes, which boosted the applications of these complexes in organic synthesis. − …”

Section: Introductionmentioning

confidence: 99%

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Dirhodium(II)/Phosphine Catalyst with Chiral Environment at Bridging Site and Its Application in Enantioselective Atropisomer Synthesis

et al. 2023

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A dirhodium(II)/phosphine catalyst with a chiral environment at the bridging site was developed for the asymmetric arylation of phenanthrene-9,10-diones with arylboronic acids. In contrast to the classic chiral bridging carboxylic acid (or derivatives) ligand strategy of bimetallic dirhodium(II) catalysis, in this reaction, tuning both axial and bridging ligands realized the first Rh 2 (OAc) 4 /phosphine-catalyzed highly enantioselective carbonyl addition reaction. The kinetic analysis reveals that dirhodium(II) and arylboronic acid follow the first-order kinetics, while phenanthrene-9,10-dione is zeroth-order. These data supported the proposed catalytic cycle, where the key intermediate in the rate-determining step involved the dirhodium(II) complex and arylboronic acid. Finally, axially chiral biaryls were prepared based on a newly developed oxidative ring-opening reaction of αhydroxyl ketones with a base and molecular oxygen, which featured a central-to-axial chirality transfer radical β-scission step.

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Section: Resultssupporting

confidence: 78%

Section: ■ Introductionsupporting

confidence: 78%

Section: Introductionmentioning

confidence: 99%

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Dirhodium(II)/Phosphine Catalyst with Chiral Environment at Bridging Site and Its Application in Enantioselective Atropisomer Synthesis

et al. 2023

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“…The first report of a bis(phenyl) dirhodium(III) paddlewheel complex formed via oxidative arylation of a Rh 2 (II,III) species came from the Doyle group ( C2 ) . Since then, their group has investigated other bisaryl complexes of the form Rh 2 (L) 4 (aryl) 2 ( C3 ). − Interestingly, in these examples, the Rh–Rh bond is absent as a result of a drastic change in the electronic structure of the Rh 2 core to π 4 δ 2 π* 4 δ* 2 . Until recently, the only example of an M 2 L 4 (aryl) n compound with an intact M–M bond and unperturbed paddlewheel came from the laboratories of Bear and Kadish ( C4 ) …”

Section: Introductionmentioning

confidence: 99%

Bisaryl Diruthenium(III) Paddlewheel Complexes: Synthesis and Characterization

Raghavan

Ren

2019

Organometallics

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Aryls represent a class of both σ- and π-donating electron-rich axial ligands that is underexplored in the field of metal–metal multiply bonded paddlewheel species. By a decrease in the steric bulk around the diruthenium axial sites and an increase in the basicity of the bridging ligands, the first examples of bisaryl diruthenium(III) paddlewheel complexes have been isolated. Compounds of the form Ru2(DMBA)4Ar2 (DMBA = N,N′-dimethylbenzamidinate, Ar = C6H4-4- t Bu (1), C6H5 (2), C6H3-3,5-(OCH3)2 (3)) were synthesized via a lithium–halogen exchange reaction between Ru2(DMBA)4Cl2 and excess LiAr and characterized using mass spectrometry, electronic absorption spectroscopy, cyclic and differential pulse voltammetry, and 1H NMR spectroscopy. The molecular structures of compounds 1–3 were established using single-crystal X-ray diffraction analysis and their electronic structures (both ground and excited state) analyzed using density functional theory calculations.

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“…The X‐ray structures of 4‐SnP and 4‐BP (Figure 1, Table 1) offer important additional insights into the chiral environment. When looking down the P–E (E=Sn, B) vector, an unusual paddlewheel‐like16 axial‐chiral structure is evident. The central phosphastannin cycle adopts a boat conformation whereas the phosphaborin cycle is more planar but strongly puckered.…”

Section: Methodsmentioning

confidence: 99%

Diferrocenophosphaborin: A Planar‐Chiral, Redox‐Active and Anion‐Responsive Ambiphilic Ligand

et al. 2015

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An ew class of Janus-like ambiphilic ligands is introduced. The rigid diferrocene backbone in heterocycles 4-SnP and 4-BP creates an unprecedented chiral environment as demonstrated by multinuclear NMR and single-crystal X-ray studies.I na ddition, the ligands are redox-responsive and the Lewis acidic borane moiety in 4-BP can be exploited to further tune the properties:aclear decrease in the CO stretching frequency of aV aska-type Rh I complex 5-BP is observed upon addition of fluoride ions.Thus,the Lewis acid and Lewis base sites influence each other and their strength can be modulated by redox chemistry and anion binding.

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Does an Axial Propeller Shape on a Dirhodium(III,III) Core Affect Equatorial Ligand Chirality?

Cited by 9 publications

References 21 publications

Dirhodium(II)/Phosphine Catalyst with Chiral Environment at Bridging Site and Its Application in Enantioselective Atropisomer Synthesis

Dirhodium(II)/Phosphine Catalyst with Chiral Environment at Bridging Site and Its Application in Enantioselective Atropisomer Synthesis

Bisaryl Diruthenium(III) Paddlewheel Complexes: Synthesis and Characterization

Diferrocenophosphaborin: A Planar‐Chiral, Redox‐Active and Anion‐Responsive Ambiphilic Ligand

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