Bismut in der Dynamisch Kovalenten Chemie: Makrocyclen und Siebenkernige Komplexkationen mit Ungewöhnlichen Strukturen DOI Creative Commons

Andreas Stoy,

Malte Jürgensen,

Christina Millidoni

и другие.

Angewandte Chemie, Год журнала: 2023, Номер 135(41)

Опубликована: Июль 31, 2023

Abstract Dynamisch kovalente Chemie (DCvC) ist ein wertvolles und breit eingesetztes Werkzeug in der modernen Synthesechemie, das auf dem reversiblen Knüpfen Brechen kovalenter Bindungen basiert. Eine inhärenten Stärken dieses Ansatzes Potential, einfachen Syntheseprotokollen reversibel neue Strukturmotive generieren zu können, die mit anderen Methoden nur schwer oder gar nicht zugänglich sind eine Vielzahl von Bindungsbrüchen ‐knüpfungen erfordern. Bislang diese fundamentalen synthesechemischen konzeptionellen Herausforderungen DCvC verstärkt leichteren p‐Block‐Elementen angegangen worden, obwohl schwerere p‐Block‐Elemente angesichts geringer Bindungsdissoziationsenergien ideal geeignet für den Einsatz erscheinen. Wir zeigen hier, dass zweikernige metallorganische Bismutverbindung, bestehend aus zwei Thioxanthen‐verbrückten BiMe 2 ‐Einheiten, bereitwillig selektive reversible Bi−C Bindungsbrüche vollzieht, wenn sie externen Stimuli ausgesetzt wird. Das Ausnutzen metallorganischen schwerer p‐block‐Elemente gewährt Zugang präzedenzlosen Makrocyclen oligonuklearen Komplexen Fass‐ähnlicher Struktur.

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

и другие.

Angewandte Chemie International Edition, Год журнала: 2023, Номер 62(24)

Опубликована: Фев. 27, 2023

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.

Язык: Английский

Процитировано

31
Small molecule activation by well-defined compounds of heavy p-block elements DOI

Kai Oberdorf,

Crispin Lichtenberg

Chemical Communications, Год журнала: 2023, Номер 59(52), С. 8043 - 8058

Опубликована: Янв. 1, 2023

Recent advances in the activation of small molecules with well-defined molecular compounds heavy p-block elements (with a principle quantum number n > 4) are summarized, highlighting key strategies, challenges, and opportunities.

Язык: Английский

Процитировано

29
Lewis Superacidic Heavy Pnictaalkene Cations: Comparative Assessment of Carbodicarbene-Stibenium and Carbodicarbene-Bismuthenium Ions DOI
Levi S. Warring, Jacob E. Walley, Diane A. Dickie

и другие.

Inorganic Chemistry, Год журнала: 2022, Номер 61(46), С. 18640 - 18652

Опубликована: Ноя. 9, 2022

We report a comprehensive assessment of Lewis acidity for series carbone-stibenium and -bismuthenium ions using the Gutmann-Beckett (GB) method. These new antimony bismuth cations have been synthesized by halide abstractions from (CDC)PnBr3 [(pyCDC)PnBr2][Br] (CDC = carbodicarbene; Pn Sb or Bi; py pyridyl). The reaction (CDC)SbBr3 (1) with one two equivalents AgNTf2 (NTf2 bis(trifluoromethanesulfonyl)imide) AgSbF6 gives stibaalkene mono- dications form [(CDC)SbBr3-n][A]n (2-4; n 1,2; A NTf2 SbF6). trication [(CDC)2Sb][NTf2]3 (5) was also isolated collectively these molecules fill gap among cationic pnictaalkenes. are compared to related CDC-bismaalkene complexes 6-9. With goal preparing highly acidic compounds, tridentate bis(pyridine)carbodicarbene (pyCDC) used as ligand access (10, 12) trications [(pyCDC)Pn][NTf2]3 (Pn (11), Bi (13)), forgoing need second CDC in synthesis 5. bonding situation is elucidated through electron density energy decomposition analyses combination natural orbital chemical valence theory. In each complex, there exists CDC-Pn double interaction, consisting strong σ-bond weaker π-bond, whereby π-bond gradually strengthens increase charge complex. Notably, [(CDC)SbBr][NTf2]2 (4) has an acceptor number (AN) (84) that comparable quintessential acids such BF3, tricationic pnictaalkene 11 13 exhibit ANs 109 Sb) 84 Bi), respectively, which highest values reported any cation. Moreover, calculated fluoride ion affinities (FIAs) 99.8 94.3 kcal/mol, larger than SbF5 (85.1 kcal/mol), suggest superacids.

Язык: Английский

Процитировано

36
Bismuth Cations: Fluoride Ion Abstraction, Isocyanide Coordination, and Impact of Steric Bulk on Lewis Acidity DOI Creative Commons
Tobias Dunaj,

Johannes Schwarzmann,

Jacqueline Ramler

и другие.

Chemistry - A European Journal, Год журнала: 2023, Номер 29(30)

Опубликована: Март 8, 2023

Abstract The molecular compound [BiDipp 2 (SbF 6 )], containing the bulky, donor‐free bismuth cation ] + has been synthesized and fully characterized (Dipp=2,6‐ i Pr ‐C H 3 ). Using its methyl analog [BiMe )] as a second reference point, impact of steric bulk on bismuth‐based Lewis acidity was investigated in combined experimental (Gutmann‐Beckett modified Gutmann‐Beckett methods) theoretical approach (DFT calculations). Reactivity studies cations towards [PF − neutral bases such isocyanides C≡NR’ revealed facile fluoride ion abstraction straightforward pair formation, respectively. first examples compounds featuring bismuth‐bound have isolated characterized.

Язык: Английский

Процитировано

14
Bismuth-based Lewis acidity DOI
Crispin Lichtenberg

Advances in inorganic chemistry, Год журнала: 2023, Номер unknown, С. 237 - 260

Опубликована: Янв. 1, 2023

Язык: Английский

Процитировано

9
Nitrogen-Based Ligands in the Coordination Sphere of Bismuth DOI
Axel Schulz

Structure and bonding, Год журнала: 2025, Номер unknown

Опубликована: Янв. 1, 2025

Язык: Английский

Процитировано

0
Environmentally Friendly Organic Synthesis Using Bismuth(III) Compounds: A Mini Review DOI

Rem Quintin V. David,

Sophie C. Thorp,

Ram S. Mohan

и другие.

Structure and bonding, Год журнала: 2025, Номер unknown

Опубликована: Янв. 1, 2025

Язык: Английский

Процитировано

0
Charge Makes a Difference: Molecular Ionic Bismuth Compounds DOI Creative Commons
Johanna Heine, Benjamin Peerless, Stefanie Dehnen

и другие.

Angewandte Chemie, Год журнала: 2023, Номер 135(24)

Опубликована: Фев. 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.

Язык: Английский

Процитировано

7
Coordination Chemistry of the Antimony(III) and Bismuth(III) Cations using Bis(α‐iminopyridine) as Ligand DOI

Hritwik Haldar,

Cem B. Yildiz, Moumita Majumdar

и другие.

ChemPlusChem, Год журнала: 2023, Номер 88(7)

Опубликована: Июль 1, 2023

Bis(alpha-iminopyridine) L has been employed as the redox non-innocent Schiff-base ligand to coordinate with cationic antimony(III) and bismuth(III) centers. Mono- di- compounds: [LSbCl2 ][CF3 SO3 ] 1, [LBiCl2 2, ]2 [Sb2 Cl8 3, [Bi2 4, [LSbCl][CF3 5, [LBiCl][CF3 6 have isolated characterized using single crystal X-ray crystallography in solid-state solution-state NMR studies. These compounds prepared from PnCl3 (Pn=Sb, Bi) chloride abstracting agent such Me3 SiCF3 or AgCF3 presence of L. The Bi tri-cationic species forms heteroleptic compound 7, being coordinated by two types donors L'. latter situ generated cleavage one imines present

Язык: Английский

Процитировано

4
Exploring Bismuth Coordination Complexes as Visible-Light Absorbers: Synthesis, Characterization, and Photophysical Properties DOI Creative Commons
Harsh Bhatia, Junjun Guo, Christopher N. Savory

и другие.

Inorganic Chemistry, Год журнала: 2023, Номер 63(1), С. 416 - 430

Опубликована: Дек. 15, 2023

Bismuth-based coordination complexes are advantageous over other metal complexes, as bismuth is the heaviest nontoxic element with high spin–orbit coupling and potential optoelectronics applications. Herein, four halide-based [Bi2Cl6(phen-thio)2] (1), [Bi2Br6(phen-thio)2] (2), [Bi2I6(phen-thio)2] (3), [Bi2I6(phen-Me)2] (4) were synthesized, characterized, subjected to detailed photophysical studies. The characterized by single-crystal X-ray diffraction, powder NMR Spectroscopic analyses of 1–4 in solutions different polarities performed understand role organic inorganic components determining ground- excited-state properties complexes. ground-state absorption, steady-state photoluminescence, microsecond time-resolved absorption spectroscopy. Periodic density functional theory (DFT) calculations on solid-state structures parts studies showed that changing ancillary ligand from chlorine (Cl) bromine (Br) iodine (I) bathochromically shifts band along enhancing coefficient. Also, halides (Cl, Br I) affects photoluminescent quantum yields ligand-centered (LC) emissive state without markedly affecting lifetimes. combined results confirmed strongly influenced part, lower-energy excited LC. This study paves way design novel for optoelectronic applications rigorously choosing ligands salt.

Язык: Английский

Процитировано

4