Carbonylation Reactions of Intramolecular Vicinal Frustrated Phosphane/Borane Lewis Pairs

被引：74

作者：

Sajid, Muhammad ^{[1
]}

Lawzer, Arunlibertsen ^{[2
]}

Dong, Weishi ^{[1
]}

Rosorius, Christoph ^{[1
]}

Sander, Wolfram ^{[2
]}

Schirmer, Birgitta ^{[1
]}

Grimme, Stefan ^{[3
]}

Daniliuc, Constantin G. ^{[1
]}

Kehr, Gerald ^{[1
]}

Erker, Gerhard ^{[1
]}

机构：

[1] Univ Munster, Inst Organ Chem, D-48149 Munster, Germany

[2] Ruhr Univ Bochum, Fac Chem & Biochem, D-44801 Bochum, Germany

[3] Univ Bonn, Mulliken Ctr Theoret Chem, Inst Phys & Theoret Chem, D-53115 Bonn, Germany

来源：

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY | 2013年 / 135卷 / 49期

基金：

欧洲研究理事会;

关键词：

HETEROLYTIC DIHYDROGEN ACTIVATION; FREE CATALYTIC-HYDROGENATION; CARBON-MONOXIDE; ELECTRONIC CONTROL; ALTERNATIVE LIGANDS; ADDITION-REACTIONS; QUANTUM-CHEMISTRY; MATRIX-ISOLATION; COMPLEXES; BORON;

D O I：

10.1021/ja408815k

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

The intramolecular frustrated Lewis pair (FLP) Mes(2)PCH(2)CH(2)B(C6F5)(2) 4 adds cooperatively to carbon monoxide to form the five-membered heterocyclic carbonyl compound 5. The intramolecular FLP 7 contains an exo-3-B(C6F5)(2) Lewis acid and an endo-2-PMes(2) Lewis base functionality coordinated at the norbornane framework. This noninteracting FLP adds carbon monoxide in solution at -35 degrees C cooperatively to yield a five-membered heterocyclic FLP-carbonyl compound 8. In contrast, FLP 7 is carbonylated in a CO-doped argon matrix at 25 K to selectively form a borane carbonyl 9 without involvement of the adjacent phosphanyl moiety. The free FLP 7 was generated in the gas phase from its FLPH2 product 10. A DFT study has shown that the phosphonium hydrido borate zwitterion 10 is formed exergonically in solution but tends to lose H-2 when brought into the gas phase.

引用

页码：18567 / 18574

页数：8

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