Mehlmann Paul, Mück-Lichtenfeld Christian, Tan Tristan T Y, Dielmann Fabian
Institut für Anorganische und Analytische Chemie, Westfälische Wilhelms-Universität Münster, Corrensstrasse 30, 48149, Münster, Germany.
Organisch-Chemisches Institut, Westfälische Wilhelms-Universität Münster, Corrensstrasse 40, 48149, Münster, Germany.
Chemistry. 2017 May 2;23(25):5929-5933. doi: 10.1002/chem.201604971. Epub 2016 Nov 11.
We report the synthesis and remarkable properties of the phosphine P(NIiPr) (NIiPr=1,3-diisopropyl-4,5-dimethylimidazolin-2-ylidenamino), a crystalline solid accessible through a short and scalable route. Evaluation of the electron-donor properties reveals a Tolman electronic parameter (TEP) value of 2029.7 cm for the new phosphine that is significantly lower than those of all known phosphines or even N-heterocyclic carbenes. Moreover, P(NIiPr) is more basic [pK (MeCN)=38.8] than Verkade's proazaphosphatranes, thus being the strongest reported nonionic phosphorus(III) superbase. The coordination chemistry of the new phosphine towards different metal centers has been explored, and due to its unique electron-releasing character, the phosphine is capable of capturing and cleaving the CO molecule.
我们报道了膦P(NIiPr)（NIiPr = 1,3 - 二异丙基 - 4,5 - 二甲基咪唑啉 - 2 - 亚基氨基）的合成及其显著性质，它是一种通过简短且可扩展的路线可获得的结晶固体。对其给电子性质的评估表明，这种新膦的托尔曼电子参数（TEP）值为2029.7 cm，明显低于所有已知膦甚至N - 杂环卡宾的值。此外，P(NIiPr)比韦尔卡德的原氮杂膦三环更具碱性[pK (MeCN)=38.8]，因此是已报道的最强非离子型磷(III)超强碱。已经探索了这种新膦与不同金属中心的配位化学，并且由于其独特的电子释放特性，该膦能够捕获并裂解CO分子。
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