Ring expansion vs. addition – reactivity of a cyclo-P4 complex towards pnictogenium cations DOI
Christoph Riesinger,

Alexander Erhard,

Manfred Scheer

и другие.

Chemical Communications, Год журнала: 2023, Номер 59(67), С. 10117 - 10120

Опубликована: Янв. 1, 2023

A systematic study on the reactivity of cyclo-P4 complexes [CpRTa(CO)2(η4-P4)] towards pnictogenium cations results in formation functionalised interpnictogen cations. Phosphenium ions insert into one P-P bonds to give ring-expanded cyclo-P5R2 products. In contrast, an arsenium-functionalised P4AsCy2 ligand displays interesting borderline case between ring expansion and coordination, while stibenium afford addition Tuning steric electronic properties ion shows a drastic influence reaction outcome.

Язык: Английский

Recent advances in the chemistry of isolable carbene analogues with group 13–15 elements DOI
Mian He, Chaopeng Hu, Rui Wei

и другие.

Chemical Society Reviews, Год журнала: 2024, Номер 53(8), С. 3896 - 3951

Опубликована: Янв. 1, 2024

This review provides an overview of main group carbene analogues, covering recent advancements, synthesis strategies, and the diverse reactivity elements in groups 13–15 based on their structural characteristics.

Язык: Английский

Процитировано

34

A stable rhodium-coordinated carbene with a σ 0 π 2 electronic configuration DOI
Chaopeng Hu, Xin‐Feng Wang, Jiancheng Li

и другие.

Science, Год журнала: 2024, Номер 383(6678), С. 81 - 85

Опубликована: Янв. 4, 2024

Isolable singlet carbenes have universally adopted a σ

Язык: Английский

Процитировано

25

Ph 3 PCN 2 : A stable reagent for carbon-atom transfer DOI
Taichi Koike,

Jhen-Kuei Yu,

Max M. Hansmann

и другие.

Science, Год журнала: 2024, Номер 385(6706), С. 305 - 311

Опубликована: Июль 18, 2024

Precise modification of a chemical site in molecule at the single-atom level is one most elegant yet difficult transformations chemistry. A reagent specifically designed for chemoselective introduction monoatomic carbon particularly formidable challenge. Here, we report straightforward, azide-free synthesis crystalline and isolable diazophosphorus ylide, Ph

Язык: Английский

Процитировано

20

Ligand Exchange at Carbon: Synthetic Entry to Elusive Species and Versatile Reagents DOI Creative Commons
Felix Krischer, Viktoria H. Gessner

JACS Au, Год журнала: 2024, Номер 4(5), С. 1709 - 1722

Опубликована: Апрель 15, 2024

How different is carbon compared to other elements in the periodic table? Can compounds be regarded as coordination complexes with central element undergoing a facile exchange of its ligands? Although clearly plays special role among table, recent studies have drawn parallels between bonding situation and reactivity transition metal complexes. This Perspective summarizes reports about ylidic zwitterionic that were shown exhibit ambiguous situations can interpreted donor–acceptor interactions similar bond neutral ligand. Based on this conception, ligand reactions prototypical realized at atoms, enabling new synthetic strategies for synthesis reactive species building blocks. In particular, N2, CO, phosphine ligands led development mild method accessing reagents unusual properties, such vinylidene ketenes or stable ketenyl anions, open up diverse but still poorly explored follow-up chemistry.

Язык: Английский

Процитировано

12

Diazoalkenes: From an Elusive Intermediate to a Stable Substance Class in Organic Chemistry DOI Creative Commons
Max M. Hansmann

Angewandte Chemie International Edition, Год журнала: 2023, Номер 62(35)

Опубликована: Апрель 25, 2023

Over decades diazoalkenes (R2 C=C=N2 ) were postulated as reactive intermediates in organic chemistry even though their direct spectroscopic detection proved very challenging. In the 1970/80ies several groups probed existence mainly indirectly by trapping experiments or directly matrix-isolation studies. 2021, our group and Severin reported independently synthesis characterization of first room-temperature stable diazoalkenes, which initiated a rapidly expanding research field. Up to now four different classes N-heterocyclic substituted have been reported. Their properties unique reactivity, such N2 /CO exchange utilization vinylidene precursors transition metal are presented. This review summarizes early discoveries from initial postulation transient, elusive species up recent findings derivatives.

Язык: Английский

Процитировано

22

Phosphinoyl-Substituted Ketenyl Anions: Synthesis and Substituent Effects on the Structural Properties DOI Creative Commons
Mike Jörges, Sunita Mondal, Manoj Kumar

и другие.

Organometallics, Год журнала: 2024, Номер 43(4), С. 585 - 593

Опубликована: Фев. 15, 2024

Ketenyl anions are versatile intermediates in synthetic chemistry and have recently become accessible as isolable reagents from metalated ylides by exchange of the phosphine with CO. Herein, we report on a systematic study substituent effects structure bonding situation ketenyl anions. A series phosphinoyl-substituted {[R

Язык: Английский

Процитировано

7

The Cyanoketenyl Anion [NC3O] DOI Creative Commons
Felix Krischer, V. S. V. S. N. Swamy, Kai‐Stephan Feichtner

и другие.

Angewandte Chemie International Edition, Год журнала: 2024, Номер 63(20)

Опубликована: Март 12, 2024

Abstract Cumulenes and heterocumulenes with three or more cumulative multiple bonds are usually reactive species that serve as valuable building blocks for complex molecules but tend to isomerize cyclize therefore difficult isolate. Using a mild ligand exchange reaction at the carbon in α‐metalated ylides, we have now succeeded synthesis gram‐scale isolation of elusive cyanoketenyl anion [NC 3 O] − . Despite its assumed cumulene‐like structure delocalization negative charge across whole 5‐atom molecule, it features bent geometry nucleophilic central atom. Computational studies reveal an ambiguous bonding situation anion, which can be illustrated only by combination different resonance structures. Nonetheless, remarkable stability, thus allowing storage potassium‐crown ether salt application highly functional synthetic block. The readily reacts series small form organic compounds, including industrially compounds such cyanoacetate. This work demonstrated generated novel methods open up atom‐economic pathways from abundant molecules.

Язык: Английский

Процитировано

7

Exploring Singlet Carbyne Anions and Related Low-Valent Carbon Species Utilizing a Cyclic Phosphino Substituent DOI
Chaopeng Hu, Xin‐Feng Wang, Chenyang Hu

и другие.

Accounts of Chemical Research, Год журнала: 2025, Номер unknown

Опубликована: Янв. 22, 2025

ConspectusThe advancement of synthetic methodologies is fundamentally driven by a deeper understanding the structure–reactivity relationships reactive key intermediates. Carbyne anions are compounds featuring monovalent anionic carbon possessing four nonbonding valence electrons, which were historically confined to theoretical constructs or observed solely within environment gas-phase studies. These species possess potential for applications across diverse domains chemistry and ancillary fields. This Account details our focused efforts isolate singlet carbyne explores isolation range related low-valent species. Our achievements include synthesis characterization, under normal laboratory conditions, gold-substituted free carbenes, copper anion complexes, ketenyl anions, keteniminyl stannyne. have been accomplished using bulky cyclic phosphino substituent, effectively stabilizes these species.Our journey commenced with phosphinocarbenes, characterized robust carbon–gold covalent single bond, progressed complexes carbon–copper ionic bond. was realized through synergistic combination group closed-shell electron-rich late transition metal. The robustness bond contrasts markedly susceptibility imparts behavior characteristic phosphinocarbyne coordination sphere copper, thereby enabling unique transfer reactions. tri-active ambiphilic nature in enables formation three chemical bonds at center one-pot Subsequent investigations unveiled ligand exchange reactions site, leading generation stable crystalline anions. emerge as potent synthons capable producing array derivatives. In addition, we isolated phosphinostannyne, rare carbon–tin multiple two adjacent centers. Collectively, demonstrated remarkable propensity engaging spectrum reactions, underscoring their versatility confirming utility synthesizing uncharted, main species.The insights derived from research contribute broader may provide platform future innovations chemistry, catalytic processes, novel materials. As continue explore develop this area study, hope that might follow footsteps potentially finding various fields future.

Язык: Английский

Процитировано

1

In Crystallo Wolff Rearrangement of a Metalated Diazoester: Structural Confirmation of the Singlet Carbene Wolff-Intermediate DOI Creative Commons
Ze‐Jie Lv, A. Fitterer, Regine Herbst‐Irmer

и другие.

Journal of the American Chemical Society, Год журнала: 2025, Номер unknown

Опубликована: Фев. 11, 2025

The Wolff rearrangement (WR) is widely used for the synthesis of ketenes from diazoketones and -esters. Stepwise WR reactions are proposed to proceed through transient carbonylcarbene (R–C–C(O)–R′) intermediates, which so far have evaded structural characterization. Here, a metallocarbene (PtII–C–C(O)–OEt) reported as fleeting intermediate in photoinitiated fragmentation diazoester ligand. Frozen solution crystal matrix isolation experiments enabled spectroscopic, magnetic, crystallographic, computational characterization this highly reactive species. All methods confirmed singlet ground state metallocarbene, stabilized by π interactions with carboxyl substituent, thus complementing spectroscopy studies classic organic reactions.

Язык: Английский

Процитировано

1

Stable crystalline keteniminyl anions DOI
Xin‐Feng Wang, Rui Wei,

Qiuming Liang

и другие.

Chem, Год журнала: 2025, Номер unknown, С. 102444 - 102444

Опубликована: Фев. 1, 2025

Язык: Английский

Процитировано

1