N-Heterocyclic Carbene Analogues of Thiele and Chichibabin Hydrocarbons

被引：60

作者：

Rottschaefer, Dennis ^{[1
]}

Ho, Nga Kim T. ^{[1
]}

Neumann, Beate ^{[1
]}

Stammler, Hans-Georg ^{[1
]}

van Gastel, Maurice ^{[2
]}

Andrada, Diego M. ^{[3
]}

Ghadwal, Rajendra S. ^{[1
]}

机构：

[1] Univ Bielefeld, Fak Chem, Anorgan Mol & Katalyse, Lehrstuhl Anorgan Chem & Strukturchem,Ctr Mol Mat, Univ Str 25, D-33615 Bielefeld, Germany

[2] Max Planck Inst Kohlenforsch, Kaiser Wilhelm Pl 1, D-45470 Mulheim An Der Ruhr, Germany

[3] Univ Saarland, Allgemeine & Anorgan Chem, Campus C4-1, D-66123 Saarbrucken, Germany

来源：

ANGEWANDTE CHEMIE-INTERNATIONAL EDITION | 2018年 / 57卷 / 20期

关键词：

Chichibabin's hydrocarbons; diradicaloids; diradicals; N-heterocyclic carbenes; Thiele's hydrocarbons; CATALYZED DIRECT C2-ARYLATION; SINGLET DIRADICAL CHARACTER; SHELL SINGLET; CLOSED-SHELL; BIS(TRIARYLAMINE) DICATIONS; COORDINATION CHEMISTRY; MULLERS HYDROCARBONS; ABNORMAL NHCS; MOLECULES; STATE;

D O I：

10.1002/anie.201713346

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

Stable N-heterocyclic carbene analogues of Thiele and Chichibabin hydrocarbons, [(IPr)(C6H4)(IPr)] and [(IPr)(C6H4)(2)(IPr)] (4 and 5, respectively; IPr - C{N(2,6-iPr(2)C(6)H(3))}(2)CHCH), are reported. In a nickel-catalyzed double carbenylation of 1,4-Br2C6H4 and 4,4'-Br-2(C6H4)(2) with IPr (1), [(IPr)(C6H4)(IPr)](Br)(2) (2) and [(IPr)(C6H4)(2)(IPr)](Br)(2) (3) were generated, which respectively afforded 4 and 5 as crystalline solids upon reduction with KC8. Experimental and computational studies support the semiquinoidal nature of 5 with a small singlet-triplet energy gap Delta ES-T of 10.7 kcal mol(-1), whereas 4 features more quinoidal character with a rather large Delta ES-T of 25.6 kcal mol(-1). In view of the low Delta ES-T, 4 and 5 may be described as biradicaloids. Moreover, 5 has considerable (41%) diradical character.

引用

页码：5838 / 5842

页数：5

共 67 条

[1] Diradicals
Abe, Manabu
[J]. CHEMICAL REVIEWS, 2013, 113 (09) : 7011 - 7088
[2] The chemistry of localized singlet 1,3-diradicals (biradicals): from putative intermediates to persistent species and unusual molecules with a π-single bonded character
Abe, Manabu
Ye, Jianhuai
Mishima, Megumi
[J]. CHEMICAL SOCIETY REVIEWS, 2012, 41 (10) : 3808 - 3820
[3] [Anonymous], 2014, Angew. Chem, DOI DOI 10.1002/ANGE.201309458
[4] A mixed-valence bis(diarylamino) stilbene:: crystal structure and comparison of electronic coupling with biphenyl and tolane analogues
Barlow, S
Risko, C
Coropceanu, V
Tucker, NM
Jones, SC
Levi, Z
Khrustalev, VN
Antipin, MY
Kinnibrugh, TL
Timofeeva, T
Marder, SR
Brédas, JL
[J]. CHEMICAL COMMUNICATIONS, 2005, (06) : 764 - 766
[5] BARRY BM, 2018, ANGEW CHEM, V130, P757
[6] Mono- and Bis(imidazolidinium ethynyl) Cations and Reduction of the Latter To Give an Extended Bis-1,4-([3]Cumulene)-p-carboquinoid System
Barry, Brian M.
Soper, R. Graeme
Hurmalainen, Juha
Mansikkamaki, Akseli
Robertson, Katherine N.
McClennan, William L.
Veinot, Alex J.
Roemmele, Tracey L.
Werner-Zwanziger, Ulrike
Boere, Rene T.
Tuononen, Heikki M.
Clyburne, Jason A. C.
Masuda, Jason D.
[J]. ANGEWANDTE CHEMIE-INTERNATIONAL EDITION, 2018, 57 (03) : 749 - 754
[7] Borden W.T., 1982, DIRADICALS
[8] Borden WT, 2015, ACS SYM SER, V1209, P251
[9] Stretching bonds in main group element compounds - Borderlines between biradicals and closed-shell species
Breher, Frank
[J]. COORDINATION CHEMISTRY REVIEWS, 2007, 251 (7-8) : 1007 - 1043
[10] Chi C., 2017, ANGEW CHEM, V129, P11573

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