Cyclic Hydrocarbon Frameworks Containing Two Bismuth Atoms: Towards 9,10‐Dibismaanthracene DOI Creative Commons
Dennis Rottschäfer, Sascha Reith,

Johannes Schwarzmann

et al.

Chemistry - A European Journal, Journal Year: 2023, Volume and Issue: 30(11)

Published: Dec. 20, 2023

Abstract When bismuth atoms are incorporated into cyclic organic systems, this commonly goes along with strained or distorted molecular geometries, which can be exploited to modulate the physical and chemical properties of these compounds. In six‐membered heterocycles, often accompanied by oxygen, sulfur nitrogen as a second hetero‐element. work, we present first examples rings, in two CH units replaced BiX moieties (X=Cl, Br, I), resulting dihydro‐anthracene analogs. Their behavior chemically reversible reduction reactions is explored, aiming at generation dibisma‐anthracene (bismanthrene). Heterometallic compounds (Bi/Fe, Bi/Mn) introduced potential bismanthrene surrogates, supported bismanthrene‐transfer selenium. Analytical techniques used investigate reported include NMR spectroscopy, high‐resolution mass spectrometry, single‐crystal X‐ray diffraction analyses, DFT calculations.

Language: Английский

Charge Makes a Difference: Molecular Ionic Bismuth Compounds DOI Creative Commons
Johanna Heine, Benjamin Peerless, Stefanie Dehnen

et al.

Angewandte Chemie, Journal Year: 2023, Volume and Issue: 135(24)

Published: Feb. 27, 2023

Abstract Key challenges in modern synthetic chemistry include the design of reliable, selective, and more sustainable methods, as well development promising candidates for new materials. Molecular bismuth compounds offer valuable opportunities they show an intriguing spectrum properties that is yet to be fully exploited: a soft character, rich coordination chemistry, availability broad variety oxidation states (at least +V −I) formal charges +3 −3) at Bi atoms, reversible switching between multiple states. All this paired with status non‐precious (semi−)metal good tendency towards low toxicity. Recent findings some these only come into reach, or can substantially optimized, when charged are specifically addressed. In review, essential contributions synthesis, analyses, utilization ionic highlighted.

Language: Английский

Citations

7
Reactivity of a Cationic Bismuth Amide towards Unsymmetric Heterocumulenes DOI Creative Commons

Kai Oberdorf,

Patrick Grenzer,

Pauline Pfister

et al.

ChemPlusChem, Journal Year: 2023, Volume and Issue: 88(7)

Published: Jan. 25, 2023

The reactivity of a literature-known, ring-strained bismuth amide cation towards range unsymmetric heterocumulene substrates has been investigated. Reactions with ketenes R2 C=C=O (R=Me, Ph), isocyanates R'N=C=O, and isothiocyanates R'N=C=S (R'=Ph, 4-CF3 -C6 H4 ) proceed via facile insertion the in Bi-N bond cationic amide. Unexpectedly pronounced differences regioselectivity these reactions have observed, yielding rich variety heterocycle motifs (BiC2 NC2 , BiC2 NCO, NCS, NCN), some which are unprecedented. Parameters that control identified discussed based on experimental theoretical investigations. Analytical techniques applied this work include heteronuclear two-dimensional NMR spectroscopy, IR elemental analysis, single-crystal X-ray diffraction analyses, DFT calculations.

Language: Английский

Citations

6
Fusing Triphenylbismuth and PnPh3 (Pn = P–Bi): Synthesis, Isolation, and Characterization of 9-Bisma-10-Pnictatriptycenes DOI
Dennis Rottschäfer,

Anna Pachkovska,

Xiulan Xie

et al.

Inorganic Chemistry, Journal Year: 2023, Volume and Issue: 62(44), P. 18228 - 18238

Published: Oct. 23, 2023

The first series of 9-bisma-10-pnictatriptycenes Bi(C6H4)3Pn (2-Pn, Pn = P-Bi; see graphic) has been synthesized in a two-step procedure via suitable tris(2-bromophenyl)pnictanes 1-Pn and characterized solution as well the solid state. DFT calculations suggest preferential interactions between 2-Pn soft Lewis acids lighter pnictogen donor atom. Experimental studies demonstrate that even weakest base 2-Pn, namely dibismatriptycene 2-Bi, interacts with acidic [BiMe2(SbF6)] solution. Analytical techniques include (VT-)NMR spectroscopy, DOSY NMR high-resolution mass spectrometry, single-crystal X-ray diffraction analyses, calculations.

Language: Английский

Citations

3
Cationic Bismuth Amides Add across Activated C═X Bonds (X = C, N, and S): Pronounced Solvent Effects on Reactivity and Selectivity DOI

Kai Oberdorf,

Pauline Pfister,

Patrick Grenzer

et al.

Organometallics, Journal Year: 2023, Volume and Issue: 42(10), P. 885 - 895

Published: May 8, 2023

The reactivity of a literature-known, ring-strained cationic bismuth amide toward the unsaturated substrates RN═C═NR, CS2, and acrylonitrile is reported (R = iPr, Cy, pTol). Subtle changes in polarity reaction medium (THF vs pyridine) can be exploited to selectively address two different pathways. Either dinuclear nature starting material preserved, only one substrate molecule per atoms incorporated into product, an aryl migration possible or well-defined mononuclear compounds with Bi/substrate ration 1:1 are observed. These findings correlate unexpected increase species, when solvent increased from THF pyridine, likely connected nuclearity material.

Language: Английский

Citations

2
Sulfinyl-aminotroponiminates: alkali- (Li, Na, K) and heavy-metal (Bi) complexes DOI

Anna Hanft,

Dennis Rottschäfer, Victoria V. L. Müller

et al.

Dalton Transactions, Journal Year: 2022, Volume and Issue: 51(28), P. 10809 - 10817

Published: Jan. 1, 2022

The installation of electron-withdrawing functional groups at the carbocyclic backbone aminotroponiminate (ATI) ligands is a versatile method for influencing electronic properties resulting ATI complexes. We report here Li, Na, and K salts an ligand with phenylsulfinyl substituent in backbone. It demonstrated that sulfinyl group actively contributes to coordination chemistry these complexes, effectively competing neutral donor such as thf or pyridine solid state (XRD), solution (DOSY NMR spectroscopy), gas phase (DFT). impact on redox complexes have been investigated access sodium sodiate species through ligand-induced disproportionation has studied. Transfer heavy p-block element bismuth demonstrated. Analytical techniques applied this work include multinuclear DOSY spectroscopy, cyclic voltammetry, DFT calculations, single-crystal X-ray diffraction analysis.

Language: Английский

Citations

3
Four-membered C^N chelation in main-group organometallic chemistry DOI
Ramkumar Kannan,

Vadapalli Chandrasekhar

Dalton Transactions, Journal Year: 2022, Volume and Issue: 52(5), P. 1159 - 1176

Published: Dec. 16, 2022

Main-group organometallic compounds containing four-membered C^N chelating rings are being studied because of the interest in harnessing enhanced reactivity such which arises as a result release steric strain. In this article, we have reviewed literature on these systems. This review is organised terms types ligand systems that allow assembly compounds, viz., aliphatic amine motifs, pyridine motifs and aniline motifs. addition to discussion synthesis structure, also examine applications main-group element involved. particular, involving H2 activation, carbonyl olefin reduction, C-H hydroalumination, cyanamide oligomerisation, borylation olefins heteroarenes, isocyanate activation C-C bond discussed.

Language: Английский

Citations

3
The Chlorido-Bismuth Dication: A Potent Lewis Acid Captured in a Hepta-Coordinate Species with a Stereochemically Active Lone Pair DOI Creative Commons
Ahmed Fetoh, Felipe Fantuzzi, Crispin Lichtenberg

et al.

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

Citations

0
The First Main Group Element Lewis Acid Thionyl chloride Adduct and its Chemistry DOI Creative Commons

Katharina Tölke,

Sven Porath, Beate Neumann

et al.

Angewandte Chemie, Journal Year: 2024, Volume and Issue: 136(41)

Published: July 15, 2024

Abstract Although the adduct of aluminum trichloride with thionyl chloride has been reported, no a main group element Lewis acid or organometallic compound structurally characterized. In this communication we present synthesis and reactivity ascertained tris(pentafluoroethyl)gallane as representative acid. Gallium indium compounds electron withdrawing groups, e.g. pentafluoroethyl ligand, display versatile properties. While gallates indates, [MR 4 ] − , behave weakly coordinating anions, neutral gallanes indanes, MR 3 are strong acids. Salts tetrakis(pentafluoroethyl)gallate ‐indate, [M(C 2 F 5 ) (M=Ga, In), have recently studied in detail. contrast to this, work on syntheses free superacids M(C In) is scarce underdeveloped. The hydrates (OH proved be suitable starting materials, particularly due their thermal stability. Herein report characterization reactive adducts, D], weak donor molecules (D) SOCl Me SiF. effective acidities Ga(C In(C were experimentally determined by (modified) Gutmann‐Beckett method catalytic potential showcased.

Language: Английский

Citations

0
The First Main Group Element Lewis Acid Thionyl chloride Adduct and its Chemistry DOI Creative Commons

Katharina Tölke,

Sven Porath, Beate Neumann

et al.

Angewandte Chemie International Edition, Journal Year: 2024, Volume and Issue: 63(41)

Published: July 15, 2024

Although the adduct of aluminum trichloride with thionyl chloride has been reported, no a main group element Lewis acid or organometallic compound structurally characterized. In this communication we present synthesis and reactivity ascertained tris(pentafluoroethyl)gallane as representative acid. Gallium indium compounds electron withdrawing groups, e.g. pentafluoroethyl ligand, display versatile properties. While gallates indates, [MR

Language: Английский

Citations

0
Characterization of Iminobismuthanes and Catalytic Reduction of Organic Azides via Bi(I)/Bi(III) Redox Cycling DOI Creative Commons
Hye Won Moon,

Nils Noethling,

Markus Leutzsch

et al.

Angewandte Chemie, Journal Year: 2024, Volume and Issue: unknown

Published: Oct. 24, 2024

Abstract We report the stoichiometric and catalytic reactivity of organobismuth(I) complexes with organic azides. Treatment N,C,N ‐pincer bismuthinidenes azides (acyl, sulfonyl, bulky aryl) results in monomeric iminobismuthanes which can be structurally characterized —including formal Bi=N double bond— by multinuclear NMR spectroscopy single‐crystal X‐ray diffraction. Building upon iminobismuthanes, reduction a broad range is developed. DFT calculations reaction pathway support redox nature overall process.

Language: Английский

Citations

0