The Viability of C5-Protonated- and C4,C5-Ditopic Carbanionic Abnormal NHCs: A New Dimension in NHC Chemistry

Rottschäfer D, Ebeler F, Strothmann T, Neumann B, Stammler H-G, Mix A, Ghadwal R (2018)
CHEMISTRY-A EUROPEAN JOURNAL 24(15): 3716-3720.

Download
Es wurde kein Volltext hochgeladen. Nur Publikationsnachweis!
Zeitschriftenaufsatz | Veröffentlicht | Englisch
Abstract / Bemerkung
The first C5-protonated abnormal N-heterocyclic carbene (aNHC), PhC{N(2,6-iPr(2)C(6)H(3))}(2)CHC: (4) is readily accessible by C4-deprotonation of [ArC{N(2,6-iPr(2)C(6)H(3))}(2)CHCH]X (3a-X) (Ar=Ph, X=Br or I) with a base. The aNHC 4 is stable at 298K in [D-8]THF solution and has been spectroscopically characterized. The facile availability of 4 enables the synthesis of a series of main-group compounds as well as transition-metal complexes featuring a new phosphorus-aNHC hybrid ligand. Double deprotonation of [ArC{N(2,6-iPr(2)C(6)H(3))}(2)CHCH]X (Ar=Ph, 3a-X (X=Br or I); 4-Tol, 3b-Br; 4-DMP, 3c-Br; Tol=MeC6H4, DMP=Me2NC6H4) with nBuLi yields the C4,C5-ditopic carbanionic aNHCs, [ArC{N(2,6-iPr(2)C(6)H(3))}(2)(C:)(2)]Li(THF)(n) (Ar=Ph, 13a; 4-Tol, 13b; 4-DMP, 13c), which on treatment with Ph2PCl affords cationic vicinal bisphosphine derivatives [ArC{N(2,6-iPr(2)C(6)H(3))}(2){C(PPh2}(2)]X (Ar=Ph, 14a-X, X=Br or I; 4-Tol, 14b-Br; 4-DMP, 14c-Br).
Erscheinungsjahr
Zeitschriftentitel
CHEMISTRY-A EUROPEAN JOURNAL
Band
24
Zeitschriftennummer
15
Seite
3716-3720
ISSN
eISSN
PUB-ID

Zitieren

Rottschäfer D, Ebeler F, Strothmann T, et al. The Viability of C5-Protonated- and C4,C5-Ditopic Carbanionic Abnormal NHCs: A New Dimension in NHC Chemistry. CHEMISTRY-A EUROPEAN JOURNAL. 2018;24(15):3716-3720.
Rottschäfer, D., Ebeler, F., Strothmann, T., Neumann, B., Stammler, H. - G., Mix, A., & Ghadwal, R. (2018). The Viability of C5-Protonated- and C4,C5-Ditopic Carbanionic Abnormal NHCs: A New Dimension in NHC Chemistry. CHEMISTRY-A EUROPEAN JOURNAL, 24(15), 3716-3720. doi:10.1002/chem.201800260
Rottschäfer, D., Ebeler, F., Strothmann, T., Neumann, B., Stammler, H. - G., Mix, A., and Ghadwal, R. (2018). The Viability of C5-Protonated- and C4,C5-Ditopic Carbanionic Abnormal NHCs: A New Dimension in NHC Chemistry. CHEMISTRY-A EUROPEAN JOURNAL 24, 3716-3720.
Rottschäfer, D., et al., 2018. The Viability of C5-Protonated- and C4,C5-Ditopic Carbanionic Abnormal NHCs: A New Dimension in NHC Chemistry. CHEMISTRY-A EUROPEAN JOURNAL, 24(15), p 3716-3720.
D. Rottschäfer, et al., “The Viability of C5-Protonated- and C4,C5-Ditopic Carbanionic Abnormal NHCs: A New Dimension in NHC Chemistry”, CHEMISTRY-A EUROPEAN JOURNAL, vol. 24, 2018, pp. 3716-3720.
Rottschäfer, D., Ebeler, F., Strothmann, T., Neumann, B., Stammler, H.-G., Mix, A., Ghadwal, R.: The Viability of C5-Protonated- and C4,C5-Ditopic Carbanionic Abnormal NHCs: A New Dimension in NHC Chemistry. CHEMISTRY-A EUROPEAN JOURNAL. 24, 3716-3720 (2018).
Rottschäfer, Dennis, Ebeler, Falk, Strothmann, Till, Neumann, Beate, Stammler, Hans-Georg, Mix, Andreas, and Ghadwal, Rajendra. “The Viability of C5-Protonated- and C4,C5-Ditopic Carbanionic Abnormal NHCs: A New Dimension in NHC Chemistry”. CHEMISTRY-A EUROPEAN JOURNAL 24.15 (2018): 3716-3720.

2 Zitationen in Europe PMC

Daten bereitgestellt von Europe PubMed Central.

N-Heterocyclic Carbene Analogues of Thiele and Chichibabin Hydrocarbons.
Rottschäfer D, Ho NKT, Neumann B, Stammler HG, van Gastel M, Andrada DM, Ghadwal RS., Angew Chem Int Ed Engl 57(20), 2018
PMID: 29668119

87 References

Daten bereitgestellt von Europe PubMed Central.


AUTHOR UNKNOWN, 0
An overview of N-heterocyclic carbenes.
Hopkinson MN, Richter C, Schedler M, Glorius F., Nature 510(7506), 2014
PMID: 24965649
N-heterocyclic carbenes: a new concept in organometallic catalysis.
Herrmann WA., Angew. Chem. Int. Ed. Engl. 41(8), 2002
PMID: 19750753

AUTHOR UNKNOWN, Angew. Chem. 114(), 2002
Heterocyclic carbenes: synthesis and coordination chemistry.
Hahn FE, Jahnke MC., Angew. Chem. Int. Ed. Engl. 47(17), 2008
PMID: 18398856

AUTHOR UNKNOWN, Angew. Chem. 120(), 2008

AUTHOR UNKNOWN, 0
Cyclic (alkyl)(amino)carbenes (CAACs): stable carbenes on the rise.
Soleilhavoup M, Bertrand G., Acc. Chem. Res. 48(2), 2014
PMID: 25515548
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 Radicals and Radical Ions.
Martin CD, Soleilhavoup M, Bertrand G., Chem Sci 4(8), 2013
PMID: 23878717
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
Ambient-temperature isolation of a compound with a boron-boron triple bond.
Braunschweig H, Dewhurst RD, Hammond K, Mies J, Radacki K, Vargas A., Science 336(6087), 2012
PMID: 22700924
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

AUTHOR UNKNOWN, 0
N-Heterocyclic Vinylidene-Stabilized Phosphorus Biradicaloid.
Rottschafer D, Neumann B, Stammler HG, Ghadwal RS., Chemistry 23(38), 2017
PMID: 28556982
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

Ezugwu, Coord. Chem. Rev. 307(), 2016
A tailored organometallic-inorganic hybrid mesostructured material: a route to a well-defined, active, and reusable heterogeneous iridium-NHC catalyst for H/D exchange.
Maishal TK, Alauzun J, Basset JM, Coperet C, Corriu RJ, Jeanneau E, Mehdi A, Reye C, Veyre L, Thieuleux C., Angew. Chem. Int. Ed. Engl. 47(45), 2008
PMID: 18846518

AUTHOR UNKNOWN, Angew. Chem. 120(), 2008

AUTHOR UNKNOWN, 0
The measure of all rings--N-heterocyclic carbenes.
Droge T, Glorius F., Angew. Chem. Int. Ed. Engl. 49(39), 2010
PMID: 20715233

AUTHOR UNKNOWN, Angew. Chem. 122(), 2010

Liske, Organometallics 32(), 2013
31P NMR chemical shifts of carbene-phosphinidene adducts as an indicator of the π-accepting properties of carbenes.
Back O, Henry-Ellinger M, Martin CD, Martin D, Bertrand G., Angew. Chem. Int. Ed. Engl. 52(10), 2013
PMID: 23364832

AUTHOR UNKNOWN, Angew. Chem. 125(), 2013
Quantifying and understanding the steric properties of N-heterocyclic carbenes.
Gomez-Suarez A, Nelson DJ, Nolan SP., Chem. Commun. (Camb.) 53(18), 2017
PMID: 28203667

AUTHOR UNKNOWN, 0

AUTHOR UNKNOWN, Angew. Chem. 117(), 2005
The use of the sterically demanding IPr* and related ligands in catalysis.
Izquierdo F, Manzini S, Nolan SP., Chem. Commun. (Camb.) 50(95), 2014
PMID: 25155373
Accessing Low-Valent Inorganic Cations by Using an Extremely Bulky N-Heterocyclic Carbene.
Roy MMD, Lummis PA, Ferguson MJ, McDonald R, Rivard E., Chemistry 23(47), 2017
PMID: 28703433
Synthesis of a Carbodicyclopropenylidene: A Carbodicarbene based Solely on Carbon.
Pranckevicius C, Liu L, Bertrand G, Stephan DW., Angew. Chem. Int. Ed. Engl. 55(18), 2016
PMID: 27028936

AUTHOR UNKNOWN, Angew. Chem. 128(), 2016
Stable cyclic carbenes and related species beyond diaminocarbenes.
Melaimi M, Soleilhavoup M, Bertrand G., Angew. Chem. Int. Ed. Engl. 49(47), 2010
PMID: 20836099

AUTHOR UNKNOWN, Angew. Chem. 122(), 2010

AUTHOR UNKNOWN, 0
Crystalline 1H-1,2,3-triazol-5-ylidenes: new stable mesoionic carbenes (MICs).
Guisado-Barrios G, Bouffard J, Donnadieu B, Bertrand G., Angew. Chem. Int. Ed. Engl. 49(28), 2010
PMID: 20509134

AUTHOR UNKNOWN, Angew. Chem. 122(), 2010
Imidazo[1,5-a]pyridine: a versatile architecture for stable N-heterocyclic carbenes.
Alcarazo M, Roseblade SJ, Cowley AR, Fernandez R, Brown JM, Lassaletta JM., J. Am. Chem. Soc. 127(10), 2005
PMID: 15755141

AUTHOR UNKNOWN, 0

Crabtree, Coord. Chem. Rev. 257(), 2013

Krüger, Aust. J. Chem. 64(), 2011

Arnold, Coord. Chem. Rev. 251(), 2007
Abnormal binding in a carbene complex formed from an imidazolium salt and a metal hydride complex.
Grundemann S, Kovacevic A, Albrecht M, Faller JW, Crabtree RH., Chem. Commun. (Camb.) (21), 2001
PMID: 12240147
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
Synthesis of Complexes with Abnormal "Protic" N-Heterocyclic Carbenes.
Jin H, Tan TT, Hahn FE., Angew. Chem. Int. Ed. Engl. 54(46), 2015
PMID: 26403225

AUTHOR UNKNOWN, Angew. Chem. 127(), 2015
Normal-to-abnormal rearrangement and NHC activation in three-coordinate iron(II) carbene complexes.
Day BM, Pugh T, Hendriks D, Guerra CF, Evans DJ, Bickelhaupt FM, Layfield RA., J. Am. Chem. Soc. 135(36), 2013
PMID: 23978294
A viable anionic N-heterocyclic dicarbene.
Wang Y, Xie Y, Abraham MY, Wei P, Schaefer HF 3rd, Schleyer Pv, Robinson GH., J. Am. Chem. Soc. 132(41), 2010
PMID: 20863065

AUTHOR UNKNOWN, 0

Waters, Coord. Chem. Rev. 293-294(), 2015

Nasr, Coord. Chem. Rev. 316(), 2016
Normal-to-abnormal rearrangement of an N-heterocyclic carbene with a silylene transition metal complex.
Ghadwal RS, Rottschafer D, Andrada DM, Frenking G, Schurmann CJ, Stammler HG., Dalton Trans 46(24), 2017
PMID: 28590484

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

Mix, Organometallics 29(), 2010

AUTHOR UNKNOWN, 0

Kuhn, Chem. Ber. 128(), 1995
Frustrated N-heterocyclic carbene-silylium ion Lewis pairs.
Silva Valverde MF, Theuergarten E, Bannenberg T, Freytag M, Jones PG, Tamm M., Dalton Trans 44(20), 2015
PMID: 25912291

AUTHOR UNKNOWN, 0

AUTHOR UNKNOWN, 0

AUTHOR UNKNOWN, 0
Dihydrogen activation by frustrated carbene-borane Lewis pairs: an experimental and theoretical study of carbene variation.
Kronig S, Theuergarten E, Holschumacher D, Bannenberg T, Daniliuc CG, Jones PG, Tamm M., Inorg Chem 50(15), 2011
PMID: 21718018
Reactions of phosphines with electron deficient boranes.
Welch GC, Prieto R, Dureen MA, Lough AJ, Labeodan OA, Holtrichter-Rossmann T, Stephan DW., Dalton Trans (9), 2009
PMID: 19421599
Frustrated Lewis pair chemistry: development and perspectives.
Stephan DW, Erker G., Angew. Chem. Int. Ed. Engl. 54(22), 2015
PMID: 25974714

AUTHOR UNKNOWN, Angew. Chem. 127(), 2015

AUTHOR UNKNOWN, 0
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

AUTHOR UNKNOWN, 0
Synthesis, structure, and applications of pyridiniophosphines.
Tinnermann H, Wille C, Alcarazo M., Angew. Chem. Int. Ed. Engl. 53(33), 2014
PMID: 24807148

AUTHOR UNKNOWN, Angew. Chem. 126(), 2014
α-Cationic phosphines: synthesis and applications.
Alcarazo M., Chemistry 20(26), 2014
PMID: 24890133

Export

Markieren/ Markierung löschen
Markierte Publikationen

Open Data PUB

Web of Science

Dieser Datensatz im Web of Science®

Quellen

PMID: 29363830
PubMed | Europe PMC

Suchen in

Google Scholar