Department of Chemistry, University of Manchester, Oxford Road, Manchester, M13 9PL, UK.
X-ray Diffraction Facility, University of Manchester, Oxford Road, Manchester, M13 9PL, UK.
Dalton Trans. 2023 Feb 21;52(8):2384-2391. doi: 10.1039/d2dt04074c.
Despite being known for decades, the solution-state molecular chemistry of heptapnictogen ([Pn]; Pn = P, As) clusters is not well established. Here we study heavy element derivatives of tetrel functionalized heptapnictogen clusters towards heteroallene capture, specifically isocyanates, an isothiocyanate and CO are probed. Clusters (MeGe)P (1), (EtGe)P (2), (BuSn)P (3), and (MeSi)As (4) were all found to capture isocyanates between all three of their tetrel-pnictogen bonds. In the case of phenyl isocyanate insertion, tetrel coordination at the isocyanate nitrogen atoms is preferred, while in the case of -toluenesulfonyl isocyanate insertion, tetrel coordination at oxygen is preferred. Furthermore, the reaction of (MeSi)P with CO gave NMR spectra consistent with the capture of the greenhouse gas. Heteroallene insertion at these clusters was also studied using density functional theory.
尽管七族元素（[Pn]；Pn = P，As）团簇的溶液态分子化学已经为人所知数十年，但尚未得到很好的确立。在这里，我们研究了四卤化硅官能化七族元素团簇的重元素衍生物，以研究其对杂烯的捕获，具体研究了异氰酸酯、异硫氰酸酯和 CO。研究发现，所有三个四卤化硅-七族元素键都可以捕获异氰酸酯，这些团簇包括（MeGe）P（1）、（EtGe）P（2）、（BuSn）P（3）和（MeSi）As（4）。在苯异氰酸酯插入的情况下，异氰酸酯氮原子上的四卤化硅配位是优选的，而在对甲苯磺酰基异氰酸酯插入的情况下，氧上的四卤化硅配位是优选的。此外，（MeSi）P 与 CO 的反应给出了与温室气体捕获一致的 NMR 谱。使用密度泛函理论也研究了这些团簇中的杂烯插入反应。
