Frustrated Lewis Pair Modification by 1,1-Carboboration: Disclosure of a Phosphine Oxide Triggered Nitrogen Monoxide Addition to an Intramolecular P/B Frustrated Lewis Pair

被引：55
作者：
Liedtke, Rene [1 ]
Scheidt, Felix [1 ]
Ren, Jinjun [2 ]
Schirmer, Birgitta [1 ]
Cardenas, Allan Jay P. [3 ]
Daniliuc, Constantin G. [1 ]
Eckert, Hellmut [2 ]
Warren, Timothy H. [3 ]
Grimme, Stefan [4 ]
Kehr, Gerald [1 ]
Erker, Gerhard [1 ]
机构：
[1] Univ Munster, Inst Organ Chem, D-48149 Munster, Germany
[2] Univ Munster, Inst Phys Chem, D-48149 Munster, Germany
[3] Georgetown Univ, Dept Chem, Washington, DC 20057 USA
[4] Univ Bonn, Inst Phys & Theoret Chem, Mulliken Ctr Theoret Chem, D-53115 Bonn, Germany
来源：
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY | 2014年 / 136卷 / 25期
基金：
美国国家科学基金会; 欧洲研究理事会;
关键词：
NITRIC-OXIDE; TRIS(PENTAFLUOROPHENYL)BORANE; BIS(PENTAFLUOROPHENYL)BORANE; 1,1-ORGANOBORATION; DERIVATIVES; B(C6F5)(3); ACTIVATION; DIHYDROGEN; CHEMISTRY; ADDUCTS;
D O I：
10.1021/ja5028293
中图分类号：
O6 [化学];
学科分类号：
0703 ;
摘要：
The vicinal frustrated Lewis pair (FLP) mes(2)P-CH2CH2B(C6F5)(2) (3) reacts with phenyl(trimethylsilyl)acetylene by 1,1-carboboration to give the extended C-3-bridged FLP 6 featuring a substituted vinylborane subunit. The FLP 6 actively cleaves dihydrogen. The FLP 3 also undergoes a 1,1-carboboration reaction with diphenylphosphino(trimethylsilyl)acetylene to give the P/B/P FLP 11 that features a central unsaturated four-membered heterocyclic P/B FLP and a pendant CH2CH2-Pmes(2) functional group. Compound 11 reacts with nitric oxide (NO) by oxidation of the pendant Pmes(2) unit to the P(O)mes(2) phosphine oxide and N,N-addition of the P/B FLP unit to NO to yield the persistent P/B/PO FLPNO aminoxyl radical 14. This reaction is initiated by P(0)mes2 formation and opening of the central Ph2P center dot center dot center dot B(C6F5)(2) linkage triggered by the pendant CH2CH2 P(O)mes(2) group.
引用
收藏
页码：9014 / 9027
页数：14
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