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Crystalline Radicals Derived from Classical N‐Heterocyclic Carbenes
Angewandte Chemie International Edition ( IF 16.1 ) Pub Date : 2018-03-15 , DOI: 10.1002/anie.201801596 Dennis Rottschäfer 1 , Beate Neumann 1 , Hans-Georg Stammler 1 , Maurice van Gastel 2 , Diego M. Andrada 3 , Rajendra S. Ghadwal 1
Angewandte Chemie International Edition ( IF 16.1 ) Pub Date : 2018-03-15 , DOI: 10.1002/anie.201801596 Dennis Rottschäfer 1 , Beate Neumann 1 , Hans-Georg Stammler 1 , Maurice van Gastel 2 , Diego M. Andrada 3 , Rajendra S. Ghadwal 1
Affiliation
One‐electron reduction of C2‐arylated 1,3‐imidazoli(ni)um salts (IPrAr)Br (Ar=Ph, 3 a; 4‐DMP, 3 b; 4‐DMP=4‐Me2NC6H4) and (SIPrAr)I (Ar=Ph, 4 a; 4‐Tol, 4 b) derived from classical NHCs (IPr=:C{N(2,6‐iPr2C6H3)}2CHCH, 1; SIPr=:C{N(2,6‐iPr2C6H3)}2CH2CH2, 2) gave radicals [(IPrAr)]. (Ar=Ph, 5 a; 4‐DMP, 5 b) and [(SIPrAr)]. (Ar=Ph, 6 a; 4‐Tol, 6 b). Each of 5 a,b and 6 a,b exhibited a doublet EPR signal, a characteristic of monoradical species. The first solid‐state characterization of NHC‐derived carbon‐centered radicals 6 a,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.
中文翻译:
源自经典N杂环卡宾的结晶自由基
单电子还原C2芳基化的1,3-咪唑啉(ni)盐(IPr Ar)Br(Ar = Ph,3 a ; 4-DMP,3 b ; 4-DMP = 4-Me 2 NC 6 H 4)和(SIPr Ar)I(Ar = Ph,4 a ; 4-Tol,4 b)源自经典NHC(IPr =:C {N(2,6 - i Pr 2 C 6 H 3)} 2 CHCH,1 ; SIPR =:C {N(2,6-我镨2 ç 6 ħ 3)} 2 CH 2 CH 2,2)给出了基团[(IPr Ar)] 。(Ar = Ph,5 a ; 4-DMP,5 b)和[(SIPr Ar)] 。(Ar = Ph,6 a ; 4-Tol,6 b)。每5,b和6,b显示出双峰EPR信号,单价物种的特性。NHC衍生的碳中心自由基6 a,b的首次固态表征据报道单晶X射线衍射。DFT计算表明,未成对的电子主要位于原始的卡宾碳原子上,并通过相邻芳基上的部分离域作用而稳定下来。
更新日期:2018-03-15
中文翻译:
源自经典N杂环卡宾的结晶自由基
单电子还原C2芳基化的1,3-咪唑啉(ni)盐(IPr Ar)Br(Ar = Ph,3 a ; 4-DMP,3 b ; 4-DMP = 4-Me 2 NC 6 H 4)和(SIPr Ar)I(Ar = Ph,4 a ; 4-Tol,4 b)源自经典NHC(IPr =:C {N(2,6 - i Pr 2 C 6 H 3)} 2 CHCH,1 ; SIPR =:C {N(2,6-我镨2 ç 6 ħ 3)} 2 CH 2 CH 2,2)给出了基团[(IPr Ar)] 。(Ar = Ph,5 a ; 4-DMP,5 b)和[(SIPr Ar)] 。(Ar = Ph,6 a ; 4-Tol,6 b)。每5,b和6,b显示出双峰EPR信号,单价物种的特性。NHC衍生的碳中心自由基6 a,b的首次固态表征据报道单晶X射线衍射。DFT计算表明,未成对的电子主要位于原始的卡宾碳原子上,并通过相邻芳基上的部分离域作用而稳定下来。