Hypervalent organobismuth complexes: pathways toward improved reactivity, catalysis, and applications

Dalton Transactions, Journal Year: 2023, Volume and Issue: 52(36), P. 12597 - 12603

Published: Jan. 1, 2023

Hypervalent (three-center, four-electron) bonding in organobismuth complexes has demonstrated to activate bonds and perturb electron configurations promoting synthesis, catalysis, materials, other applications.

Language: Английский

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Structures, Bonding Analyses and Reactivity of a Dicationic Digallene and Diindene Mimicking trans‐bent Ditetrylenes

Angewandte Chemie International Edition, Journal Year: 2023, Volume and Issue: 62(47)

Published: Sept. 20, 2023

The reaction of bisdicyclohexylphosphinoethane (dcpe) and the subvalent M

Language: Английский

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Rational Design of Metallylenes for Hydrogenation Reactions

European Journal of Organic Chemistry, Journal Year: 2024, Volume and Issue: 27(14)

Published: Feb. 12, 2024

Abstract The hydrogenation of alkenes, alkynes, carbonyls, and imines by H 2 ‐activated metallylenes (H 3 C−EH −L, CELH ; E =Si, Ge, Sn L =NMe , PMe ) was studied using relativistic density functional theory at ZORA‐BP86/TZ2P. By means activation strain Kohn–Sham molecular orbital analyses, the physical factors underlying trends in reactivity were identified quantified. Firstly, increases on descending Group 14, that is from silylenes ( =Si) to stannylenes =Sn). This trend originates primarily a reduced energy required break bonds between 14 atom hydrogen atoms because strength these decreases Si−H Ge−H Sn−H. Secondly, as 15 ligand changes nitrogen phosphorus which stems trigonal pyramidal geometry compared planar NMe geometry. latter can, therefore, effectively engage stronger interactions with substrate than former, due more efficient HOMO–LUMO overlap. combining our insights, we rationally designed an optimally tuned catalyst (Group ligand) considering overall catalytic cycle involving metallylene subsequent hydrogenation.

Language: Английский

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From Neutral Diarsenes to Diarsene Radical Ions and Diarsene Dications

Chemistry - A European Journal, Journal Year: 2024, Volume and Issue: 30(25)

Published: Feb. 23, 2024

Abstract Diarsene [L(MeO)GaAs] 2 (L=HC[C(Me)N(Ar)] , Ar=2,6‐ i Pr C 6 H 3 4 ) reacts with MeOTf and Me NHC ( NHC=1,3,4,5‐tetra‐methylimidazol‐2‐ylidene) to the diarsene [L(TfO)GaAs] 5 carbene‐coordinated [L(MeO)GaAsAs( NHC)Ga(OMe)L] ). The NHC‐coordination results in an inversion of redox properties which shows only a reversible reduction event at E 1/2 =−2.06 V vs Fc 0/+1 whereas oxidation =−1.31 . Single electron transfer reactions yielded [K[2.2.2.]cryp][L(MeO)GaAs] 8 NHC)‐Ga(OMe)L][B(C F ] 9 containing radical anion ⋅ − NHC‐coordinated cation NHC)Ga(OMe)L]⋅ + ), respectively, while salt‐elimination reaction triflate‐coordinated Na[B(C gave [LGaAs] [B(C 11 dication 2+ Compounds 1 – were characterized by 13 NMR, EPR IR, UV‐Vis spectroscopy single crystal X‐ray diffraction (sc‐XRD). DFT calculations provided detailed understanding electronic nature diarsenes ions respectively.

Language: Английский

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Isolation of Elusive Fluoflavine Radicals in Two Differing Oxidation States

Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: unknown

Published: Sept. 12, 2024

Facile access and switchability between multiple oxidation states are key properties of many catalytic applications spintronic devices yet poorly understood due to inherent complications arising from isolating a redox system in without drastic structural changes. Here, we present the first isolable, free fluoflavine (flv) radical flv(

Language: Английский

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Reductive Coupling of a Diazoalkane Derivative Promoted by a Potassium Aluminyl and Elimination of Dinitrogen to Generate a Reactive Aluminium Ketimide

Chemistry - A European Journal, Journal Year: 2023, Volume and Issue: 29(71)

Published: Oct. 3, 2023

Abstract The reaction of 9‐diazo‐9 H ‐fluorene (fluN 2 ) with the potassium aluminyl K[Al(NON)] ([NON] 2− =[O(SiMe NDipp) ] , Dipp=2,6‐ i Pr C 6 3 affords K[Al(NON)(κ N 1 ‐{(fluN })] ( ). Structural analysis shows a near planar 1,4‐di(9 ‐fluoren‐9‐ylidene)tetraazadiide ligand that chelates to aluminium. thermally induced elimination dinitrogen from neutral aluminium ketimide complex, Al(NON)(N=flu)(THF) and 1,2‐di(9 ‐fluoren‐9‐yl)diazene dianion as salt, [K (THF) ][fluN=Nflu] N’ ‐di iso propylcarbodiimide PrN=C=N Pr) guanidinate Al(NON){N( Pr)C(N=CMe )N(CHflu)} 4 ), showing rare example reactivity at metal ligand. Density functional theory (DFT) calculations have been used examine bonding in newly formed [(fluN . mechanism leading formation has also studied using this technique.

Language: Английский

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Bismuth in Radical Chemistry and Catalysis

Angewandte Chemie, Journal Year: 2023, Volume and Issue: 136(8)

Published: Nov. 22, 2023

Abstract Whereas indications of radical reactivity in bismuth compounds can be traced back to the 19 th century, preparation and characterization both transient persistent bismuth‐radical species has only been established recent decades. These advancements led emergence field chemistry, mirroring progress seen for other main‐group elements. The seminal fundamental studies this area have ultimately paved way development catalytic methodologies involving intermediates, a promising approach that remains largely untapped broad landscape synthetic organic chemistry. In review, we delve into milestones eventually present state‐of‐the‐art Our focus aims at outlining intrinsic discoveries inorganic/organometallic chemistry contextualizing their practical applications synthesis catalysis.

Language: Английский

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Activation of heteroallenes by metal-substituted electron-rich tetrylenes

Polyhedron, Journal Year: 2023, Volume and Issue: 247, P. 116702 - 116702

Published: Oct. 28, 2023

The metal-substituted germylene LGa(μ–Cl)GeDMP (L = HC[C(Me)NDipp]2, Dipp 2,6-iPr2C6H3, DMP 2,6-Mes2C6H3, Mes 2,4,6-Me3C6H2) 1 reacts with CO2 reductive decarbonylation and formation of the oxygen-bridged complex L(Cl)GaOGeDMP 2, which was also formed in reaction N2O. most likely proceeds via intermediate a gallacarboxylate as is observed reactions both ethyl isocyanate N,N'-dicyclohexylcarbodiimide, yielding corresponding heteroallenes insertion complexes L(Cl)Ga-[C(NEt)O]-GeDMP 3 L(Cl)Ga-[C(NCy)2]-GeDMP 4. In addition, gallanediyle stannylene adduct LGa-Sn[N(SiMe3)(Dipp)] 5 to form tin L(Cl)Ga-(CO2)-Sn[N(Dipp)(SiMe3)] 6. Complexes 2–4 6 are characterized spectroscopically (1H, 13C, 119Sn (6), IR) by single crystal X-ray diffraction (sc-XRD).

Language: Английский

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Crystallographic evidence for Bi(I) as the heaviest halogen bond acceptor

Published: Dec. 28, 2023

Complexation of a bismuthinidene (RBi) with two equivalents highly fluorinated aryl iodide at low temperature al-lows the crystallographic identification an unstable species that can be regarded as intermediate oxidative addition reaction. Both C-I bonds are orientated towards filled 6p orbital bismuth (Bi-I distances 3.44-3.52 Å), leading to elongation by 0.05 and 0.07 Å. DFT calculations confirm center is indeed acting electron donor, establishing strong directional halogen bonds. As such, this study presents first structural proof bismuth, (and more generally heavy organopnictogen compounds in oxidation state +1), bond acceptors.

Language: Английский

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The Chlorido-Bismuth Dication: A Potent Lewis Acid Captured in a Hepta-Coordinate Species with a Stereochemically Active Lone Pair

Inorganic Chemistry, Journal Year: 2024, Volume and Issue: 63(26), P. 12089 - 12099

Published: June 20, 2024

The stabilization of simple, highly reactive cationic species in molecular complexes represents an important strategy to isolate and characterize compounds with uncommon or even unprecedented structural motifs properties. Here we report the synthesis, isolation, full characterization chlorido-bismuth dications, stabilized only by monodentate dimethylsulfoxide (dmso) ligands: [BiCl(dmso)

Language: Английский

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