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Bimolecular Homolytic Substitutions at Nitrogen: An Experimental and Theoretical Study on the Gas‐Phase Reactions of Alkyl Radicals with NF3
Chemistry - A European Journal ( IF 3.9 ) Pub Date : 2015-09-08 , DOI: 10.1002/chem.201501757
Paola Antoniotti , Paola Benzi , Stefano Borocci , Chiara Demaria , Maria Giordani , Felice Grandinetti , Lorenza Operti , Roberto Rabezzana

The X‐ray irradiation of binary mixtures of alkyl iodides RI (R=CH3, C2H5, or i‐C3H7 radicals) and NF3 produces RNF2 and RF. Based on calculations performed at the CCSD(T), MRCI(SD+Q), G3B3, and G3 levels of theory, the former product arises from a bimolecular homolytic substitution reaction (SH2) by the alkyl radicals R, which attack the N atom of NF3. This mechanism is consistent with the suppression of RNF2 by addition of O2 (an efficient alkyl radical scavenger) to the reaction mixture. The RF product arises from the attack of R to the F atom of NF3, but additional contributing channels are conceivably involved. The F‐atom abstraction is, indeed, considerably more exothermic than the SH2 reaction, but the involved energy barriers are comparable, and the two processes are comparably fast.

中文翻译:

氮的双分子均溶取代:烷基自由基与NF3气相反应的实验和理论研究

的二元混合物的X射线照射烷基碘- [R I(R = CH 3,C 2 H ^ 5,或-C 3 ħ 7组的基团)和NF 3产生R NF 2和R F.根据计算以CCSD(T),MRCI(SD + Q),G3B3和G3的理论水平进行反应时,前一种产物是由烷基R攻击烷基的N原子引起的双分子均溶取代反应(S H 2)产生的。 NF 3。这种机制是与抑制的R一致 NF 2通过加入的O 2(有效的烷基自由基清除剂)加入反应混合物中。将R F产品源于R与NF的F原子的攻击3,但额外贡献通道可以想象参与。F-原子的提取确实比S H 2反应放热大得多,但是所涉及的能垒是可比的,并且两个过程相当快。
更新日期:2015-09-08
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