Isolation and characterization of a triplet nitrene DOI Creative Commons
Gengwen Tan, Dongmin Wang, Wang Chen

et al.

Research Square (Research Square), Journal Year: 2024, Volume and Issue: unknown

Published: June 14, 2024

Abstract Free nitrenes of R–N are short-lived intermediates in a variety nitrogen-involved transformations. They feature either singlet ground state or triplet state, depending on the electronic properties substituents R. Triplet arylnitrenes typically undergo facile ring expansion to azacycloheptatetraenes, making their isolation condensed phase highly challenging. Herein, we present synthesis, and characterization an isolable arylnitrene supported by bulky hydrindacene ligand. The high stability is largely attributed sufficient steric hindrance effective electron delocalization imparted supporting Electron paramagnetic resonance spectroscopy conjunction with correlated wavefunction based ab initio calculations unambiguously demonstrated its axial zero-field splitting D = 0.92 cm–1 vanishing rhombicity E/D 0.002. This work not only presents long-sought reaction intermediate, but also provides in-depth insights into mechanisms involving nitrenes.

Language: Английский

An Isolable One‐Coordinate Lead(I) Radical with Strong g‐Factor Anisotropy DOI
Haonan Chen, Wang Chen, Dongmin Wang

et al.

Angewandte Chemie International Edition, Journal Year: 2024, Volume and Issue: 63(20)

Published: March 5, 2024

Abstract Lead‐based radicals in the oxidation state of +1 are elusive species and highly challenging to isolate condensed phase. In this study, we present synthesis characterization first isolable free plumbylyne radical 2 bearing a one‐coordinate Pb(I) atom. It reacts with an N ‐heterocyclic carbene (NHC) afford two‐coordinate NHC‐ligated 3 . represent Pb(I)‐based radicals. Theoretical calculations electron paramagnetic resonance analysis revealed that unpaired mainly resides at Pb 6p orbital both Owing unique nature atom , it possesses two‐fold pseudo‐degeneracy substantial unquenched angular momentum, exhibits hitherto strongest g ‐factor anisotropy ( x,y,z =1.496, 1.166, 0.683) amongst main group Preliminary investigations into reactivity unveiled its Pb‐centered nature, plumbylenes were isolated as products.

Language: Английский

Citations

11
Isolation and characterization of a triplet nitrene DOI
Dongmin Wang, Wang Chen, Haonan Chen

et al.

Nature Chemistry, Journal Year: 2024, Volume and Issue: 17(1), P. 38 - 43

Published: Nov. 19, 2024

Language: Английский

Citations

10
Molecular-strain induced phosphinidene reactivity of a phosphanorcaradiene DOI Creative Commons
Yizhen Chen, Peifeng Su, Dongmin Wang

et al.

Nature Communications, Journal Year: 2024, Volume and Issue: 15(1)

Published: May 29, 2024

Abstract Phosphanorcaradienes are an appealing class of phosphorus compounds that can serve as synthons transient phosphinidenes. However, the synthesis such species is a formidable task owing to their intrinsic high reactivity. Herein we report straightforward synthesis, characterization and reactivity studies phosphanorcaradiene, in which one benzene rings flanking fluorenyl substituents intramolecularly dearomatized through attachment atom. It facilely obtained by reduction phosphorus(III) dichloride precursor with potassium graphite. Despite being thermally robust, it acts synthetic equivalent phosphinidene. reacts trimethylphosphine isonitrile yield phosphanylidene-phosphorane 1-phospha-3-azaallene, respectively. When treated two molar equivalents azide, iminophosphane bis(imino)phosphane isolated, Moreover, capable activating ethylene alkyne afford [1 + 2] cycloaddition products, well oxidative cleavage Si–H N–H bonds secondary phosphines. All reactions proceed smoothly at room temperature without presence transition metals. The driving force for these most likely ring-constraint three-membered PC 2 ring recovery aromaticity ring.

Language: Английский

Citations

6
Synthesis and magnetic property of a telluryl radical DOI
Dongmin Wang, Wang Chen, Rong Sun

et al.

Chem, Journal Year: 2025, Volume and Issue: unknown, P. 102392 - 102392

Published: Jan. 1, 2025

Language: Английский

Citations

0
Crystalline Arylstibinidene Chalcogenides: Heavier Congeners of Aromatic Nitroso Compounds DOI
Xinyi Li, Yizhen Chen, Shicheng Dong

et al.

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

Published: March 10, 2025

Nitroso compounds, R-N═O, containing N═O double bonds are ubiquitous and widely utilized in organic synthesis. In contrast, heavier congeners of nitroso namely pnictinidene chalcogenides R-Pn = E (Pn P, As, Sb, Bi; O, S, Se, Te), highly reactive scarce. They have been stabilized the coordination sphere Lewis acid/base or by pronounced contribution from resonance structures, whereas free species with unperturbed pnictogen-chalcogen remains elusive. this work, we report isolation characterization arylstibinidene chalcogenides, which first aromatic compounds. facilely synthesized through salt metathesis reactions aryldichlorostibane dilithium chalcogenides. bear Sb═E (E Se Te) due to poor orbital overlap between C 2p orbitals phenyl ring substituent Sb 5p orbitals. Moreover, they show versatile reactivity, including acting as chalcogen atom transfer reagents reacting small molecules via (cyclo)addition.

Language: Английский

Citations

0
Molecular-Strain Driven Phosphinidene Reactivity of a Phosphanorcaradiene DOI Creative Commons
Gengwen Tan, Yizhen Chen, Dongmin Wang

et al.

Published: Jan. 17, 2024

Herein we report straightforward synthesis, characterization and reactivity studies of a phosphanorcaradiene, in which one the benzene rings flanking fluorenyl substituents is intramolecularly dearomatized through attachment to phosphorus atom. It was facilely obtained by reduction phosphorus(III) dichloride MsFluidtBu-PCl2 supported hydrindacene substituent with potassium graphite. Despite being thermally robust, it serves as an elegant precursor for transient phosphinidene. reacted trimethylphosphine isonitrile yield phosphanylidene-phosphorane 1-phospha-3-azaallene, respectively. Moreover, capable activating ethylene 4-tertbutylphenylacetylene afford [1+2] cycloaddition products, well oxidative cleavage Si–H N–H bonds secondary phosphines. All reactions proceeded smoothly at room temperature without presence transition metals. The driving force these most likely high ring-constraint three-membered PC2 ring recovery aromaticity ring.

Language: Английский

Citations

3
Aromative Dephosphinidenation of a Bisphosphirane‐Fused Anthracene toward E‐H (E = H, Si, N and P) Bond Activation DOI
Qing Luo, Tingting Liu,

Linlin Huang

et al.

Angewandte Chemie International Edition, Journal Year: 2024, Volume and Issue: 63(46)

Published: Aug. 1, 2024

Abstract A bisphosphirane‐fused anthracene ( 5 ) was prepared by treatment of a sterically encumbered amino phosphorus dichloride 3 with Mg ⋅ THF =anthracene). X‐ray diffraction analysis revealed pentacyclic framework consisting two phosphirane rings fused to the in trans ‐fashion. Compound has been shown be an efficient phosphinidene synthon, readily liberating transient units for subsequent downstream bond activation via reductive elimination under mild conditions. The formal oxidative addition H 2 and E−H (E=Si, N, P) bonds liberated provided diphosphine substituted phosphines. Furthermore, transfer alkenes alkynes smoothly yielded corresponding phosphiranes phosphirenes. mechanism investigated density functional theory (DFT) calculations.

Language: Английский

Citations

2
Aromative Dephosphinidenation of a Bisphosphirane‐Fused Anthracene toward E‐H (E = H, Si, N and P) Bond Activation DOI Open Access
Qing Luo, Tingting Liu,

Linlin Huang

et al.

Angewandte Chemie, Journal Year: 2024, Volume and Issue: 136(46)

Published: Aug. 1, 2024

Abstract A bisphosphirane‐fused anthracene ( 5 ) was prepared by treatment of a sterically encumbered amino phosphorus dichloride 3 with Mg ⋅ THF =anthracene). X‐ray diffraction analysis revealed pentacyclic framework consisting two phosphirane rings fused to the in trans ‐fashion. Compound has been shown be an efficient phosphinidene synthon, readily liberating transient units for subsequent downstream bond activation via reductive elimination under mild conditions. The formal oxidative addition H 2 and E−H (E=Si, N, P) bonds liberated provided diphosphine substituted phosphines. Furthermore, transfer alkenes alkynes smoothly yielded corresponding phosphiranes phosphirenes. mechanism investigated density functional theory (DFT) calculations.

Language: Английский

Citations

0
Synthesis and Characterization of Diarylgermanethione and Diarylgermaneselenone DOI
Yizhen Chen, Gengwen Tan

European Journal of Inorganic Chemistry, Journal Year: 2024, Volume and Issue: 27(34)

Published: Sept. 30, 2024

Abstract Lewis acid/base‐free diarylgermanethione 3 and diarylgermaneselenone 4 were synthesized through reactions of a heteroleptic diarylgermylene with elemental sulfur selenium, respectively. They fully characterized by structural, spectroscopic computational methods. Germanethione underwent 1,2‐addition AlMe at the Ge=S double to give Ge(IV) compound 5 . The chalcogen atoms in could coordinate copper halide yield Cu(I) complexes 6 7 ,

Language: Английский

Citations

0
An Isolable One‐Coordinate Lead(I) Radical with Strong g‐Factor Anisotropy DOI
Haonan Chen, Wang Chen, Dongmin Wang

et al.

Angewandte Chemie, Journal Year: 2024, Volume and Issue: 136(20)

Published: March 5, 2024

Abstract Lead‐based radicals in the oxidation state of +1 are elusive species and highly challenging to isolate condensed phase. In this study, we present synthesis characterization first isolable free plumbylyne radical 2 bearing a one‐coordinate Pb(I) atom. It reacts with an N ‐heterocyclic carbene (NHC) afford two‐coordinate NHC‐ligated 3 . represent Pb(I)‐based radicals. Theoretical calculations electron paramagnetic resonance analysis revealed that unpaired mainly resides at Pb 6p orbital both Owing unique nature atom , it possesses two‐fold pseudo‐degeneracy substantial unquenched angular momentum, exhibits hitherto strongest g ‐factor anisotropy ( x,y,z =1.496, 1.166, 0.683) amongst main group Preliminary investigations into reactivity unveiled its Pb‐centered nature, plumbylenes were isolated as products.

Language: Английский

Citations

0