Sn(<scp>ii</scp>)–carbon bond reactivity: radical generation and consumption <i>via</i> reactions of a stannylene with alkynes

Zou, Wenxing; Mears, Kristian L.; Fettinger, James C.; Power, Philip P.

doi:10.1039/d3cc04014c

Chem. Commun.

2023

DOI: 10.1039/d3cc04014c

|View full text |Cite

Sn(ii)–carbon bond reactivity: radical generation and consumption via reactions of a stannylene with alkynes

Wenxing Zou,

Kristian L. Mears,

James C. Fettinger

et al.

Abstract: Thermal Sn–C cleavage in the diarylstannylene Sn(AriPr4)2 (AriPr4 = C6H3-2,6-(C6H3-2,6-iPr2)2) was used to generate ·Sn(AriPr4) and ·AriPr4 radicals for alkyne arylstannylation. The radical pair and RCCR (R = H, R...

Help me understand this report

Search citation statements

Order By: Relevance

Paper Sections

Select...

Citation Types

Supporting

Mentioning

Contrasting

Year Published

2024

Publication Types

Select...

Article4

Relationship

Self Cite0

Independent4

Authors

Journals

Cited by 4 publications

References 42 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

An Isolable One‐Coordinate Lead(I) Radical with Strong g‐Factor Anisotropy

Chen,

Wang

et al. 2024

Angewandte Chemie

View full text Add to dashboard Cite

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

show abstract

An Isolable One‐Coordinate Lead(I) Radical with Strong g‐Factor Anisotropy

Chen,

Wang

et al. 2024

Angewandte Chemie

View full text Add to dashboard Cite

show abstract

Aktivierung von Diorganyl‐bis(pyridylimino)isoindolid‐Aluminiumkomplexen mit sichtbarem Licht und deren organometallische Radikalreaktivität

Wenzel,

Werner,

Allgaier

et al. 2024

Angewandte Chemie

View full text Add to dashboard Cite

We report on the synthesis and characterization of a series of (mostly) air‐stable diorganyl bis(pyridylimino) isoindolide (BPI) aluminum complexes and their chemistry upon visible‐light excitation. The redox non‐innocent BPI pincer ligand allows for efficient charge transfer homolytic processes of the title compounds. This makes them a universal platform for the generation of carbon‐centered radicals. The photo‐induced homolytic cleavage of the Al–C bonds was investigated by means of stationary and transient UV/Vis spectroscopy, spin trapping experiments, as well as EPR and NMR spectroscopy. The experimental findings were supported by quantum chemical calculations. Reactivity studies enabled the utilization of the aluminum complexes as reactants in tin‐free Giese‐type reactions and carbonyl alkylations under ambient conditions, which both indicated radical‐polar crossover behavior. A deeper understanding of the physical fundamentals and photochemical process was provided, furnishing in turn a new strategy to control the reactivity of bench‐stable aluminum organometallics.

show abstract

An Isolable One‐Coordinate Lead(I) Radical with Strong g‐Factor Anisotropy

Chen,

Wang

et al. 2024

Angew Chem Int Ed

View full text Add to dashboard Cite

show abstract

scite is a Brooklyn-based organization that helps researchers better discover and understand research articles through Smart Citations–citations that display the context of the citation and describe whether the article provides supporting or contrasting evidence. scite is used by students and researchers from around the world and is funded in part by the National Science Foundation and the National Institute on Drug Abuse of the National Institutes of Health.

Contact Info

customersupport@researchsolutions.com

10624 S. Eastern Ave., Ste. A-614

Henderson, NV 89052, USA

This site is protected by reCAPTCHA and the Google Privacy Policy and Terms of Service apply.

Blog Terms and Conditions API Terms Privacy Policy Contact Cookie Preferences Do Not Sell or Share My Personal Information

Made with 💙 for researchers

Part of the Research Solutions Family.

Sn(ii)–carbon bond reactivity: radical generation and consumption via reactions of a stannylene with alkynes

Abstract: Thermal Sn–C cleavage in the diarylstannylene Sn(AriPr4)2 (AriPr4 = C6H3-2,6-(C6H3-2,6-iPr2)2) was used to generate ·Sn(AriPr4) and ·AriPr4 radicals for alkyne arylstannylation. The radical pair and RCCR (R = H, R...

Cited by 4 publications

References 42 publications

An Isolable One‐Coordinate Lead(I) Radical with Strong g‐Factor Anisotropy

An Isolable One‐Coordinate Lead(I) Radical with Strong g‐Factor Anisotropy

Aktivierung von Diorganyl‐bis(pyridylimino)isoindolid‐Aluminiumkomplexen mit sichtbarem Licht und deren organometallische Radikalreaktivität

An Isolable One‐Coordinate Lead(I) Radical with Strong g‐Factor Anisotropy

Contact Info

Product

Resources

About