Indirect synthesis of a pair of formal methane activation products at a phosphane/borane frustrated Lewis pair

被引：8
|
作者：
Froemel, Silke [1 ]
Daniliuc, Constantin G. [1 ]
Bannwarth, Christoph [2 ]
Grimme, Stefan [2 ]
Bussmann, Kathrin [1 ]
Kehr, Gerald [1 ]
Erker, Gerhard [1 ]
机构：
[1] Univ Munster, Inst Organ Chem, Corrensstr 40, D-48149 Munster, Germany
[2] Univ Bonn, Inst Phys & Theoret Chem, Mulliken Ctr Theoret Chem, Beringstr 4, D-53115 Bonn, Germany
来源：
DALTON TRANSACTIONS | 2016年 / 45卷 / 48期
关键词：
ZETA-VALENCE QUALITY; C-H BORYLATION; POLYMERIZATION CATALYSTS; OLEFIN POLYMERIZATION; NITRIC-OXIDE; BASIS-SETS; CHEMISTRY; REACTIVITY; COMPLEXES; HYDROGEN;
D O I：
10.1039/c6dt04206f
中图分类号：
O61 [无机化学];
学科分类号：
070301 ; 081704 ;
摘要：
The regioisomeric formal Mes(2)PCH(2)CH(2)B(C6F5)(2) FLP methane splitting products Mes(2)P(H)CH2CH2B(CH3)(C6F5)(2) and Mes(2)P(CH3) CH2CH2B(H)(C6F5)(2) were produced by indirect stepwise reactions. They were stable at 60 degrees C and were both characterized by X-ray diffraction. A DFT analysis revealed that their formation from the FLP and CH4 would be endergonic by +6.9 and +3.6 kcal mol(-1), respectively, and it indicated that methane elimination from the zwitterionic products is kinetically hindered by barriers of 54.0 and 72.3 kcal mol(-1), respectively.
引用
收藏
页码：19230 / 19233
页数：4
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