Crystalline Radicals Derived from Classical N-Heterocyclic Carbenes

Rottschäfer D, Neumann B, Stammler H-G, van Gastel M, Andrada DM, Ghadwal R (2018)
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION 57(17): 4765-4768.

Zeitschriftenaufsatz | Veröffentlicht | Englisch
 
Download
Es wurden keine Dateien hochgeladen. Nur Publikationsnachweis!
Abstract / Bemerkung
One-electron reduction of C2-arylated 1,3-imidazoli(ni)um salts (IPrAr)Br (Ar=Ph, 3a; 4-DMP, 3b; 4-DMP=4-Me2NC6H4) and (SIPrAr)I (Ar=Ph, 4a; 4-Tol, 4b) derived from classical NHCs (IPr=:C{N(2,6-iPr(2)C(6)H(3))}(2)CHCH, 1; SIPr=:C{N(2,6-iPr(2)C(6)H(3))}(2)CH2CH2, 2) gave radicals [(IPrAr)](center dot) (Ar=Ph, 5a; 4-DMP, 5b) and [(SIPrAr)](center dot) (Ar=Ph, 6a; 4-Tol, 6b). Each of 5a,b and 6a,b exhibited a doublet EPR signal, a characteristic of monoradical species. The first solid-state characterization of NHC-derived carbon-centered radicals 6a,b by single-crystal X-ray diffraction is reported. DFT calculations indicate that the unpaired electron is mainly located at the original carbene carbon atom and stabilized by partial delocalization over the adjacent aryl group.
Stichworte
density functional calculations; EPR spectroscopy; N-heterocyclic; carbenes; radicals; X-ray diffraction
Erscheinungsjahr
2018
Zeitschriftentitel
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
Band
57
Ausgabe
17
Seite(n)
4765-4768
ISSN
1433-7851
eISSN
1521-3773
Page URI
https://pub.uni-bielefeld.de/record/2920269

Zitieren

Rottschäfer D, Neumann B, Stammler H-G, van Gastel M, Andrada DM, Ghadwal R. Crystalline Radicals Derived from Classical N-Heterocyclic Carbenes. ANGEWANDTE CHEMIE-INTERNATIONAL EDITION. 2018;57(17):4765-4768.
Rottschäfer, D., Neumann, B., Stammler, H. - G., van Gastel, M., Andrada, D. M., & Ghadwal, R. (2018). Crystalline Radicals Derived from Classical N-Heterocyclic Carbenes. ANGEWANDTE CHEMIE-INTERNATIONAL EDITION, 57(17), 4765-4768. doi:10.1002/anie.201801596
Rottschäfer, Dennis, Neumann, Beate, Stammler, Hans-Georg, van Gastel, Maurice, Andrada, Diego M., and Ghadwal, Rajendra. 2018. “Crystalline Radicals Derived from Classical N-Heterocyclic Carbenes”. ANGEWANDTE CHEMIE-INTERNATIONAL EDITION 57 (17): 4765-4768.
Rottschäfer, D., Neumann, B., Stammler, H. - G., van Gastel, M., Andrada, D. M., and Ghadwal, R. (2018). Crystalline Radicals Derived from Classical N-Heterocyclic Carbenes. ANGEWANDTE CHEMIE-INTERNATIONAL EDITION 57, 4765-4768.
Rottschäfer, D., et al., 2018. Crystalline Radicals Derived from Classical N-Heterocyclic Carbenes. ANGEWANDTE CHEMIE-INTERNATIONAL EDITION, 57(17), p 4765-4768.
D. Rottschäfer, et al., “Crystalline Radicals Derived from Classical N-Heterocyclic Carbenes”, ANGEWANDTE CHEMIE-INTERNATIONAL EDITION, vol. 57, 2018, pp. 4765-4768.
Rottschäfer, D., Neumann, B., Stammler, H.-G., van Gastel, M., Andrada, D.M., Ghadwal, R.: Crystalline Radicals Derived from Classical N-Heterocyclic Carbenes. ANGEWANDTE CHEMIE-INTERNATIONAL EDITION. 57, 4765-4768 (2018).
Rottschäfer, Dennis, Neumann, Beate, Stammler, Hans-Georg, van Gastel, Maurice, Andrada, Diego M., and Ghadwal, Rajendra. “Crystalline Radicals Derived from Classical N-Heterocyclic Carbenes”. ANGEWANDTE CHEMIE-INTERNATIONAL EDITION 57.17 (2018): 4765-4768.

3 Zitationen in Europe PMC

Daten bereitgestellt von Europe PubMed Central.

Kekulé diradicaloids derived from a classical N-heterocyclic carbene.
Rottschäfer D, Neumann B, Stammler HG, Andrada DM, Ghadwal RS., Chem Sci 9(22), 2018
PMID: 29938024
Unveiling the redox-active character of imidazolin-2-thiones derived from amino-substituted N-heterocyclic carbenes.
Ruamps M, Bastin S, Rechignat L, Sournia-Saquet A, Valyaev DA, Mouesca JM, Lugan N, Maurel V, César V., Chem Commun (Camb) 54(55), 2018
PMID: 29932183
Silanylidene and Germanylidene Anions: Valence-Isoelectronic Species to the Well-Studied Phosphinidene.
Siddiqui MM, Sinhababu S, Dutta S, Kundu S, Ruth PN, Münch A, Herbst-Irmer R, Stalke D, Koley D, Roesky HW., Angew Chem Int Ed Engl 57(36), 2018
PMID: 29975006

66 References

Daten bereitgestellt von Europe PubMed Central.


Renaud, 2001

Halliwell, 2015

AUTHOR UNKNOWN, 0
Diradicals.
Abe M., Chem. Rev. 113(9), 2013
PMID: 23883325

Salem, Angew. Chem. Int. Ed. Engl. 11(), 1972

AUTHOR UNKNOWN, Angew. Chem. 84(), 1972
Odd-electron bonds and biradicals in main group element chemistry.
Grutzmacher H, Breher F., Angew. Chem. Int. Ed. Engl. 41(21), 2002
PMID: 12412065

AUTHOR UNKNOWN, Angew. Chem. 114(), 2002

Morita, 2010

Konu, 2010

AUTHOR UNKNOWN, 0
An overview of N-heterocyclic carbenes.
Hopkinson MN, Richter C, Schedler M, Glorius F., Nature 510(7506), 2014
PMID: 24965649
Silylene-Functionalized N-Heterocyclic Carbene (Si-NHC).
Rottschafer D, Blomeyer S, Neumann B, Stammler HG, Ghadwal RS., Chemistry 24(2), 2017
PMID: 28833705

AUTHOR UNKNOWN, 0
Dichlorosilylene: a high temperature transient species to an indispensable building block.
Ghadwal RS, Azhakar R, Roesky HW., Acc. Chem. Res. 46(2), 2012
PMID: 23181482
N-heterocyclic carbene-main-group chemistry: a rapidly evolving field.
Wang Y, Robinson GH., Inorg Chem 53(22), 2014
PMID: 25343222
Carbene-stabilized main group diatomic allotropes.
Wang Y, Robinson GH., Dalton Trans 41(2), 2011
PMID: 21904737

AUTHOR UNKNOWN, 0
Electron paramagnetic resonance and computational studies of radicals derived from boron-substituted N-heterocyclic carbene boranes.
Walton JC, Brahmi MM, Monot J, Fensterbank L, Malacria M, Curran DP, Lacote E., J. Am. Chem. Soc. 133(26), 2011
PMID: 21619055
N-heterocyclic carbene boryl radicals: a new class of boron-centered radical.
Ueng SH, Solovyev A, Yuan X, Geib SJ, Fensterbank L, Lacote E, Malacria M, Newcomb M, Walton JC, Curran DP., J. Am. Chem. Soc. 131(31), 2009
PMID: 19606860
Generation and Structure of Unique Boriranyl Radicals.
Walton JC, McFadden TR, Curran DP., J. Am. Chem. Soc. 139(46), 2017
PMID: 29099598

AUTHOR UNKNOWN, 0
Cyclic (Alkyl)(amino)carbenes (CAACs): Recent Developments.
Melaimi M, Jazzar R, Soleilhavoup M, Bertrand G., Angew. Chem. Int. Ed. Engl. 56(34), 2017
PMID: 28376253

AUTHOR UNKNOWN, Angew. Chem. 129(), 2017
Cyclic (alkyl)(amino)carbenes (CAACs): stable carbenes on the rise.
Soleilhavoup M, Bertrand G., Acc. Chem. Res. 48(2), 2014
PMID: 25515548
Carbene-Stabilized Main Group Radicals and Radical Ions.
Martin CD, Soleilhavoup M, Bertrand G., Chem Sci 4(8), 2013
PMID: 23878717
Silicon based radicals, radical ions, diradicals and diradicaloids.
Chandra Mondal K, Roy S, Roesky HW., Chem Soc Rev 45(4), 2015
PMID: 26585359
Modular Approach to Kekule Diradicaloids Derived from Cyclic (Alkyl)(amino)carbenes.
Hansmann MM, Melaimi M, Munz D, Bertrand G., J. Am. Chem. Soc. 140(7), 2018
PMID: 29382199
Organic Mixed Valence Compounds Derived from Cyclic (Alkyl)(amino)carbenes.
Hansmann MM, Melaimi M, Bertrand G., J. Am. Chem. Soc. 140(6), 2018
PMID: 29342351

AUTHOR UNKNOWN, 0
What can NMR spectroscopy of selenoureas and phosphinidenes teach us about the π-accepting abilities of N-heterocyclic carbenes?
Vummaleti SVC, Nelson DJ, Poater A, Gomez-Suarez A, Cordes DB, Slawin AMZ, Nolan SP, Cavallo L., Chem Sci 6(3), 2015
PMID: 29449918
Estimation of σ-Donation and π-Backdonation of Cyclic Alkyl(amino) Carbene-Containing Compounds.
Mondal KC, Roy S, Maity B, Koley D, Roesky HW., Inorg Chem 55(1), 2015
PMID: 26675319

Viehe, Acc. Chem. Res. 18(), 1985

AUTHOR UNKNOWN, 0
Trapping a Silicon(I) Radical with Carbenes: A Cationic cAAC-Silicon(I) Radical and an NHC-Parent-Silyliumylidene Cation.
Li Y, Chan YC, Leong BX, Li Y, Richards E, Purushothaman I, De S, Parameswaran P, So CW., Angew. Chem. Int. Ed. Engl. 56(26), 2017
PMID: 28544030

AUTHOR UNKNOWN, Angew. Chem. 129(), 2017
α-Radical Phosphines: Synthesis, Structure, and Reactivity.
Gu L, Zheng Y, Haldon E, Goddard R, Bill E, Thiel W, Alcarazo M., Angew. Chem. Int. Ed. Engl. 56(30), 2017
PMID: 28544330

AUTHOR UNKNOWN, Angew. Chem. 129(), 2017
Reagent for Introducing Base-Stabilized Phosphorus Atoms into Organic and Inorganic Compounds.
Kundu S, Sinhababu S, Luebben AV, Mondal T, Koley D, Dittrich B, Roesky HW., J. Am. Chem. Soc. 140(1), 2017
PMID: 29266940
Organosilicon Radicals with Si-H and Si-Me Bonds from Commodity Precursors.
Kundu S, Samuel PP, Sinhababu S, Luebben AV, Dittrich B, Andrada DM, Frenking G, Stuckl AC, Schwederski B, Paretzki A, Kaim W, Roesky HW., J. Am. Chem. Soc. 139(32), 2017
PMID: 28745880
Main-Group Metallomimetics: Transition Metal-like Photolytic CO Substitution at Boron.
Braunschweig H, Krummenacher I, Legare MA, Matler A, Radacki K, Ye Q., J. Am. Chem. Soc. 139(5), 2017
PMID: 28103028

AUTHOR UNKNOWN, 0
Bottleable (amino)(carboxy) radicals derived from cyclic (alkyl)(amino) carbenes.
Mahoney JK, Martin D, Moore CE, Rheingold AL, Bertrand G., J. Am. Chem. Soc. 135(50), 2013
PMID: 24304381
Crystalline Monomeric Allenyl/Propargyl Radical.
Hansmann MM, Melaimi M, Bertrand G., J. Am. Chem. Soc. 139(44), 2017
PMID: 29046060
Crystalline Cyclic (Alkyl)(amino)carbene-tetrafluoropyridyl Radical.
Styra S, Melaimi M, Moore CE, Rheingold AL, Augenstein T, Breher F, Bertrand G., Chemistry 21(23), 2015
PMID: 25925367
Air-persistent monomeric (amino)(carboxy) radicals derived from cyclic (alkyl)(amino) carbenes.
Mahoney JK, Martin D, Thomas F, Moore CE, Rheingold AL, Bertrand G., J. Am. Chem. Soc. 137(23), 2015
PMID: 26011769

AUTHOR UNKNOWN, 0
Neutral Aminyl Radicals Derived from Azoimidazolium Dyes.
Eymann LY, Tskhovrebov AG, Sienkiewicz A, Bila JL, Zivkovic I, Ronnow HM, Wodrich MD, Vannay L, Corminboeuf C, Pattison P, Solari E, Scopelliti R, Severin K., J. Am. Chem. Soc. 138(46), 2016
PMID: 27933881
Triazenyl Radicals Stabilized by N-Heterocyclic Carbenes.
Back J, Park J, Kim Y, Kang H, Kim Y, Park MJ, Kim K, Lee E., J. Am. Chem. Soc. 139(43), 2017
PMID: 29037041
A Stable Anionic Dithiolene Radical.
Wang Y, Hickox HP, Xie Y, Wei P, Blair SA, Johnson MK, Schaefer HF 3rd, Robinson GH., J. Am. Chem. Soc. 139(20), 2017
PMID: 28482154
The reactions of imidazol-2-ylidenes with the hydrogen atom: a theoretical study and experimental confirmation with muonium.
McKenzie I, Brodovitch JC, Percival PW, Ramnial T, Clyburne JA., J. Am. Chem. Soc. 125(38), 2003
PMID: 13129359

AUTHOR UNKNOWN, 0

Rottschäfer, Chem. Eur. J. (), 2018
Facile routes to abnormal-NHC-cobalt(ii) complexes.
Ghadwal RS, Lamm JH, Rottschafer D, Schurmann CJ, Demeshko S., Dalton Trans 46(24), 2017
PMID: 28573296

Ho, Catalysts 7(), 2017

Rottschäfer, Organometallics 35(), 2016

Ghadwal, Z. Anorg. Allg. Chem. 642(), 2016
Isolation of a C5-deprotonated imidazolium, a crystalline "abnormal" N-heterocyclic carbene.
Aldeco-Perez E, Rosenthal AJ, Donnadieu B, Parameswaran P, Frenking G, Bertrand G., Science 326(5952), 2009
PMID: 19900893

AUTHOR UNKNOWN, 0
Nickel-catalysed direct C2-arylation of N-heterocyclic carbenes.
Ho NKT, Neumann B, Stammler HG, Menezes da Silva VH, Watanabe DG, Braga AAC, Ghadwal RS., Dalton Trans 46(36), 2017
PMID: 28853488
1,3-Bis(2,6-diisopropyl-phen-yl)imidazolidin-2-yl-idene.
Giffin NA, Hendsbee AD, Masuda JD., Acta Crystallogr Sect E Struct Rep Online 66(Pt 9), 2010
PMID: 21588570
Material in PUB:
Teil dieser Dissertation
Export

Markieren/ Markierung löschen
Markierte Publikationen

Open Data PUB

Web of Science

Dieser Datensatz im Web of Science®
Quellen

PMID: 29465816
PubMed | Europe PMC

Suchen in

Google Scholar