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

et al.

Journal of the American Chemical Society, Journal Year: 2025, Volume and Issue: unknown

Published: Feb. 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.

Language: Английский

P–P Coupling with and without Terminal Metal–Phosphorus Intermediates DOI Creative Commons
Richard R. Thompson, Matthew T. Figgins,

Duleeka C. Wannipurage

et al.

Journal of the American Chemical Society, Journal Year: 2025, Volume and Issue: unknown

Published: Jan. 28, 2025

Terminal metal–phosphorus (M–P) complexes are of significant contemporary interest as potential platforms for P-atom transfer (PAT) chemistry. Decarbonylation metal–phosphaethynolate (M–PCO) has emerged a general synthetic approach to terminal M–P complexes. that stabilized by strong multiple bonds kinetically persistent and isolable. In the absence stabilization, formation diphosphorus-bridged (i.e., M–P–P–M species) is often interpreted evidence intermediacy reactive, unobserved species. Here, we demonstrate while diphosphorus can arise from reactive species, P–P coupling also proceed directly M–PCO species without Photochemical decarbonylations pincer-supported Ni (II)–PCO complex at 77 K afford spectroscopically observed Ni–P complex, which best described triplet, Ni(II)-metallophosphinidene with two unpaired electrons localized on atomic phosphorus ligand. Thermal annealing this transient results in rapid dimerization corresponding P22–-bridged dinickel complex. Unexpectedly, same be accessed via thermally promoted process light. The analysis reaction kinetics, isotope-labeling studies, computational indicate thermal proceeds noncanonical mechanism avoids intermediates. Together, these represent first observation characterized intermediates not required obtain products. These observations provide critical mechanistic understanding activation modes relevant transfer.

Language: Английский

Citations

2
Exploring Singlet Carbyne Anions and Related Low-Valent Carbon Species Utilizing a Cyclic Phosphino Substituent DOI
Chaopeng Hu, Xin‐Feng Wang, Chenyang Hu

et al.

Accounts of Chemical Research, Journal Year: 2025, Volume and Issue: unknown

Published: Jan. 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.

Language: Английский

Citations

0
Trendbericht Anorganische Chemie 2024: Hauptgruppen‐ und Molekülchemie DOI Open Access
Josh Abbenseth, Frank Tambornino

Nachrichten aus der Chemie, Journal Year: 2025, Volume and Issue: 73(2), P. 46 - 55

Published: Jan. 31, 2025

Abstract Das erste heterobimetallische Dimetallocen; mit sterisch anspruchsvollen Liganden lassen sich einfach‐koordinierte Hauptgruppenverbindungen der Gruppen 13 bis 15 herstellen; neue Diazoverbindungen erlauben es, B‐R‐Einheiten und Kohlenstoffatome zu übertragen.

Citations

0
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

et al.

Journal of the American Chemical Society, Journal Year: 2025, Volume and Issue: unknown

Published: Feb. 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.

Language: Английский

Citations

0