An Open-Shell Singlet Sn Diradical and H Splitting

Overview

Journal Angew Chem Int Ed Engl

Specialty Chemistry

Date 2021 Jan 18

PMID 33460280

Citations 8

Authors

Mahendra K Sharma

Dennis Rottschafer

Timo Glodde

Beate Neumann

Hans-Georg Stammler

Rajendra S Ghadwal

Affiliations

Soon will be listed here.

Abstract

The first Sn diradical [(ADC )Sn] (4) based on an anionic dicarbene (ADC ={CN(Dipp)} CPh; Dipp=2,6-iPr C H ) scaffold has been isolated as a green crystalline solid by KC reduction of the corresponding bis-chlorostannylene [(ADC )SnCl] (3). The six-membered C Sn -ring of 4 containing six π-electrons shows a diatropic ring current, thus 4 may also be regarded as the first 1,4-distannabenzene derivative. DFT calculations suggest an open-shell singlet (OS) ground state of 4 with a remarkably small singlet-triplet energy gap (ΔE =4.4 kcal mol ), which is consistent with CASSCF (ΔE =6.6 kcal mol and diradical character y=37 %) calculations. The diradical 4 splits H at room temperature to yield the bis-hydridostannylene [(ADC )SnH] (5). Further reactivity of 4 has been studied with PhSeSePh and MeOTf.

Citing Articles

Annulated carbocyclic gallylene and bis-gallylene with two-coordinated Ga(i) atoms.

Merschel A, Heda S, Vishnevskiy Y, Neumann B, Stammler H, Ghadwal R Chem Sci. 2025; 16(5):2222-2230.

PMID: 39781217 PMC: 11706234. DOI: 10.1039/d4sc06782g.

Isolation of an Anionic Dicarbene Embedded Sn P Cluster and Reversible CO Uptake.

Ebeler F, Vishnevskiy Y, Neumann B, Stammler H, Ghadwal R Adv Sci (Weinh). 2023; 11(5):e2305545.

PMID: 38018314 PMC: 10837339. DOI: 10.1002/advs.202305545.

Rational Design of Persistent Phosphorus-Centered Singlet Tetraradicals and Their Use in Small-Molecule Activation.

Zander E, Bresien J, Zhivonitko V, Fessler J, Villinger A, Michalik D J Am Chem Soc. 2023; 145(26):14484-14497.

PMID: 37315222 PMC: 10368346. DOI: 10.1021/jacs.3c03928.

Can a Wanzlick-like equilibrium exist between dicoordinate borylenes and diborenes?.

Fantuzzi F, Jiao Y, Dewhurst R, Weinhold F, Braunschweig H, Engels B Chem Sci. 2022; 13(18):5118-5129.

PMID: 35655568 PMC: 9093173. DOI: 10.1039/d1sc05988b.

Isolation of an Arsenic Diradicaloid with a Cyclic C As -Core.

Steffenfauseweh H, Vishnevskiy Y, Neumann B, Stammler H, Andrada D, Ghadwal R Angew Chem Int Ed Engl. 2022; 61(34):e202207415.

PMID: 35652361 PMC: 9545666. DOI: 10.1002/anie.202207415.

References

Abe M . Diradicals. Chem Rev. 2013; 113(9):7011-88. DOI: 10.1021/cr400056a. View

Al-Rafia S, Malcolm A, Liew S, Ferguson M, Rivard E . Stabilization of the heavy methylene analogues, GeH2 and SnH2, within the coordination sphere of a transition metal. J Am Chem Soc. 2010; 133(4):777-9. DOI: 10.1021/ja1106223. View

Bantu B, Pawar G, Decker U, Wurst K, Schmidt A, Buchmeiser M . CO2 and Sn(II) adducts of N-heterocyclic carbenes as delayed-action catalysts for polyurethane synthesis. Chemistry. 2009; 15(13):3103-9. DOI: 10.1002/chem.200802670. View

Stanger A . Nucleus-independent chemical shifts (NICS): distance dependence and revised criteria for aromaticity and antiaromaticity. J Org Chem. 2006; 71(3):883-93. DOI: 10.1021/jo051746o. View

Wang Y, Frasconi M, Stoddart J . Introducing Stable Radicals into Molecular Machines. ACS Cent Sci. 2017; 3(9):927-935. PMC: 5620985. DOI: 10.1021/acscentsci.7b00219. View

Wang X, Peng Y, Olmstead M, Fettinger J, Power P . An unsymmetric oxo/imido-bridged germanium-centered singlet diradicaloid. J Am Chem Soc. 2009; 131(40):14164-5. DOI: 10.1021/ja906053y. View

Rottschafer D, Blomeyer S, Neumann B, Stammler H, Ghadwal R . Direct functionalization of white phosphorus with anionic dicarbenes and mesoionic carbenes: facile access to 1,2,3-triphosphol-2-ides. Chem Sci. 2020; 10(48):11078-11085. PMC: 7069227. DOI: 10.1039/c9sc04441h. View

Beweries T, Kuzora R, Rosenthal U, Schulz A, Villinger A . [P(μ-NTer)]2: a biradicaloid that is stable at high temperature. Angew Chem Int Ed Engl. 2011; 50(38):8974-8. DOI: 10.1002/anie.201103742. View

Ota K, Kinjo R . Inorganic Benzene Valence Isomers. Chem Asian J. 2021; 15(17):2558-2574. DOI: 10.1002/asia.202000535. View

10.

Messelberger J, Grunwald A, Pinter P, Hansmann M, Munz D . Carbene derived diradicaloids - building blocks for singlet fission?. Chem Sci. 2018; 9(28):6107-6117. PMC: 6053972. DOI: 10.1039/c8sc01999a. View

11.

Takeuchi K, Ichinohe M, Sekiguchi A . Access to a stable Si2N2 four-membered ring with non-Kekulé singlet biradical character from a disilyne. J Am Chem Soc. 2011; 133(32):12478-81. DOI: 10.1021/ja2059846. View

12.

Hinz A, Schulz A, Villinger A . A mixed arsenic-phosphorus centered biradicaloid. Angew Chem Int Ed Engl. 2014; 54(2):668-72. DOI: 10.1002/anie.201408639. View

13.

He G, Shynkaruk O, Lui M, Rivard E . Small inorganic rings in the 21st century: from fleeting intermediates to novel isolable entities. Chem Rev. 2014; 114(16):7815-80. DOI: 10.1021/cr400547x. View

14.

Sharma M, Glodde T, Neumann B, Stammler H, Ghadwal R . Distannabarrelenes with Three Coordinated Sn Atoms. Chemistry. 2020; 26(49):11113-11118. PMC: 7496072. DOI: 10.1002/chem.202001432. View

15.

Merschel A, Glodde T, Neumann B, Stammler H, Ghadwal R . Nickel-Catalyzed Intramolecular 1,2-Aryl Migration of Mesoionic Carbenes (iMICs). Angew Chem Int Ed Engl. 2020; 60(6):2969-2973. PMC: 7898293. DOI: 10.1002/anie.202014328. View

16.

Scheschkewitz D, Amii H, Gornitzka H, Schoeller W, Bourissou D, Bertrand G . Singlet diradicals: from transition states to crystalline compounds. Science. 2002; 295(5561):1880-1. DOI: 10.1126/science.1068167. View

17.

Sharma M, Rottschafer D, Glodde T, Neumann B, Stammler H, Ghadwal R . An Open-Shell Singlet Sn Diradical and H Splitting. Angew Chem Int Ed Engl. 2021; 60(12):6414-6418. PMC: 7986611. DOI: 10.1002/anie.202017078. View

18.

Jung Y, Head-Gordon M . How diradicaloid is a stable diradical?. Chemphyschem. 2003; 4(5):522-5. DOI: 10.1002/cphc.200200668. View

19.

Sugahara T, Guo J, Hashizume D, Sasamori T, Tokitoh N . Reversible Isomerizations between 1,4-Digermabenzenes and 1,4-Digerma-Dewar-benzenes: Air-Stable Activators for Small Molecules. J Am Chem Soc. 2019; 141(6):2263-2267. DOI: 10.1021/jacs.9b00129. View

20.

Chen Z, Wannere C, Corminboeuf C, Puchta R, Schleyer P . Nucleus-independent chemical shifts (NICS) as an aromaticity criterion. Chem Rev. 2005; 105(10):3842-88. DOI: 10.1021/cr030088+. View