Sellin Malte, Rupf Susanne Margot, Abram Ulrich, Malischewski Moritz
Freie Universität Berlin, Institut für Chemie und Biochemie-Anorganische Chemie Fabeckstraße 34-36, 14195 Berlin, Germany.
Inorg Chem. 2021 Apr 19;60(8):5917-5924. doi: 10.1021/acs.inorgchem.1c00326. Epub 2021 Mar 28.
Homoleptic eightfold coordinated methyl isocyanide complexes of W(IV) and W(V) have been prepared for the first time. The reaction of [NBu][W(CN)] with methyl triflate (MeOTf) gives [W(CNMe)][OTf]. The even stronger methylating mixture of methyl fluoride (MeF) and arsenic pentafluoride (AsF) in liquid sulfur dioxide (SO) is able to fully alkylate both [NBu][W(CN)] and [NBu][W(CN)]. The paramagnetic octakis(methyl isocyanide)tungsten(V) complex [W(CNMe)][AsF] is thermally highly unstable above -30 °C. All compounds have been characterized via single-crystal X-ray diffraction and IR, Raman, and NMR or EPR spectroscopy.
首次制备了W(IV)和W(V)的全同配八重配位甲基异腈配合物。[NBu][W(CN)]与三氟甲磺酸甲酯（MeOTf）反应生成[W(CNMe)][OTf]。在液态二氧化硫（SO）中，更强的甲基化混合物——甲基氟（MeF）和五氟化砷（AsF），能够使[NBu][W(CN)]和[NBu][W(CN)]都完全烷基化。顺磁性的八（甲基异腈）钨（V）配合物[W(CNMe)][AsF]在高于-30°C时热稳定性极差。所有化合物均通过单晶X射线衍射以及红外、拉曼和核磁共振或电子顺磁共振光谱进行了表征。
