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Quantifying the Electronic and Steric Properties of 1,3-Imidazole-Based Mesoionic Carbenes (iMICs)
Organometallics ( IF 2.5 ) Pub Date : 2020-03-09 , DOI: 10.1021/acs.organomet.0c00045 Arne Merschel 1 , Dennis Rottschäfer 1 , Beate Neumann 1 , Hans-Georg Stammler 1 , Rajendra S. Ghadwal 1
Organometallics ( IF 2.5 ) Pub Date : 2020-03-09 , DOI: 10.1021/acs.organomet.0c00045 Arne Merschel 1 , Dennis Rottschäfer 1 , Beate Neumann 1 , Hans-Georg Stammler 1 , Rajendra S. Ghadwal 1
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1,3-Imidazole-based mesoionic carbenes (iMICs) are a very promising class of carbon-donor ligands in synthesis and catalysis. However, a systematic study of the quantification of stereoelectronic properties of iMICs is lacking. This is most likely due to the absence of rational synthetic routes to suitable iMIC compounds. Herein, we report the synthesis of the appropriate phosphinidene (iMICAr)PPh (iMICAr = :CCH(NDipp)2CAr; Ar = Ph (5a), DMP (5b); DMP = 4-Me2NC6H4; Dipp = 2,6-iPr2C6H3), selenium (iMICAr)Se (Ar = Ph (6a), DMP (6b)), and nickel carbonyl compounds (iMICAr)Ni(CO)3 (Ar = Ph (7a), DMP (7b)). The π-accepting property of iMICAr (Ar = Ph (2a), DMP (2b)) has been evaluated by 31P and 77Se NMR spectroscopic analyses of 5 and 6, respectively. The overall donor property of 2 has been assessed by determining the Tolman electronic parameter (TEP) of 7. Studies suggest that iMICAr (2) are stronger σ donors and weaker π acceptors compared to classical N-heterocyclic carbenes (NHCs). The steric profile of iMICAr (2) has been obtained by calculating the percentage buried volume (%Vbur) for (iMICAr)CuX (Ar = Ph, X = I (8a); Ar = DMP, X = Br (8b)).
中文翻译：
量化基于1,3-咪唑的中型羧甲基苯甲酸酯（iMIC）的电子和立体性能
1,3-咪唑基中离子碳烯（iMIC）是合成和催化中非常有前途的一类碳供体配体。然而，缺乏对iMIC的立体电子性质的定量的系统研究。这很可能是由于缺乏通往合适的iMIC化合物的合理合成途径。在这里，我们报告了适当的次膦基（iMIC Ar）PPh（iMIC Ar =：CCH（NDipp）2 CAr; Ar = Ph（5a），DMP（5b）; DMP = 4-Me 2 NC 6 H 4；浸渍= 2,6- i Pr 2 C 6 H 3），硒（iMIC ArSe（Ar = Ph（6a），DMP（6b））和羰基镍化合物（iMIC Ar）Ni（CO）3（Ar = Ph（7a），DMP（7b））。iMIC Ar（Ar = Ph（2a），DMP（2b））的π接受性质已分别通过31 P和77 Se NMR光谱法对5和6进行了评估。的总供体属性2已通过确定的托尔曼电子参数（TEP）评估7。研究表明，iMIC Ar（2）与传统的N-杂环卡宾（NHC）相比，是更强的σ供体和更弱的π受体。IMIC的立体轮廓的Ar（2）已经被计算百分比掩埋体积（％获得V BUR）为（IMIC氩）的CuX（AR =苯基，X = I（8a中的Ar = DMP，X = Br（上）8B））。
更新日期：2020-03-09
中文翻译：
量化基于1,3-咪唑的中型羧甲基苯甲酸酯（iMIC）的电子和立体性能
1,3-咪唑基中离子碳烯（iMIC）是合成和催化中非常有前途的一类碳供体配体。然而，缺乏对iMIC的立体电子性质的定量的系统研究。这很可能是由于缺乏通往合适的iMIC化合物的合理合成途径。在这里，我们报告了适当的次膦基（iMIC Ar）PPh（iMIC Ar =：CCH（NDipp）2 CAr; Ar = Ph（5a），DMP（5b）; DMP = 4-Me 2 NC 6 H 4；浸渍= 2,6- i Pr 2 C 6 H 3），硒（iMIC ArSe（Ar = Ph（6a），DMP（6b））和羰基镍化合物（iMIC Ar）Ni（CO）3（Ar = Ph（7a），DMP（7b））。iMIC Ar（Ar = Ph（2a），DMP（2b））的π接受性质已分别通过31 P和77 Se NMR光谱法对5和6进行了评估。的总供体属性2已通过确定的托尔曼电子参数（TEP）评估7。研究表明，iMIC Ar（2）与传统的N-杂环卡宾（NHC）相比，是更强的σ供体和更弱的π受体。IMIC的立体轮廓的Ar（2）已经被计算百分比掩埋体积（％获得V BUR）为（IMIC氩）的CuX（AR =苯基，X = I（8a中的Ar = DMP，X = Br（上）8B））。
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