Carbonylation reactions of intramolecular vicinal frustrated phosphane/borane Lewis pairs.
Carbonylation reactions of intramolecular vicinal frustrated phosphane/borane Lewis pairs.
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DOI：
10.1021/ja408815k
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发表时间：
2013-11
影响因子：
15
通讯作者：
M. Sajid;Arun‐Libertsen Lawzer;Weishi Dong;Christoph Rosorius;W. Sander;B. Schirmer;S. Grimme;
中科院分区：
文献类型：
--
作者：
M. Sajid;Arun‐Libertsen Lawzer;Weishi Dong;Christoph Rosorius;W. Sander;B. Schirmer;S. Grimme;
分子内阻挫刘易斯对（FLP）Mes 2 PCH 2CH 2B（C6 F5）2 4与一氧化碳协同加成形成五元杂环羰基化合物5。分子内FLP 7含有一个外-3-B（C6 F5）2刘易斯酸和一个内-2-PMes 2刘易斯碱官能团，配位在正戊烷骨架上。这种非相互作用的FLP在-35 °C下协同添加溶液中的一氧化碳，以产生五元杂环FLP-羰基化合物8。相比之下，FLP 7在CO掺杂的氩基质中在25 K下羰基化以选择性地形成硼烷羰基9而不涉及相邻的膦基部分。游离FLP 7在气相中由其FLPH 2产物10产生。DFT研究表明，双硼酸盐两性膦10在溶液中形成，但当进入气相时倾向于失去H2。
The intramolecular frustrated Lewis pair (FLP) Mes2PCH2CH2B(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-PMes2 Lewis base functionality coordinated at the norbornane framework. This noninteracting FLP adds carbon monoxide in solution at -35 °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 H2 when brought into the gas phase.