Mrózek Ondřej, Dostál Libor, Císařová Ivana, Honzíček Jan, Vinklárek Jaromír
Department of General and Inorganic Chemistry, Faculty of Chemical Technology, University of Pardubice, Studentská 573, 532 10 Pardubice, Czech Republic.
Department of Inorganic Chemistry, Faculty of Science, Charles University in Prague, Hlavova 2030/8, 128 43 Prague 2, Czech Republic.
Dalton Trans. 2019 Aug 28;48(32):12210-12218. doi: 10.1039/c9dt02229e. Epub 2019 Jul 23.
We report herein a new class of mixed propene-indenyl complexes of molybdenum and tungsten stabilized by a strong N→M intramolecular coordination. The complexes [{η:κN-1-(CHN)CH}(η-CH)M(CO)][BF] (M = Mo, W) were obtained in nearly quantitative yields by the protonation of the η-allyl ligand in compounds [(η-CH){η-1-(CHN)CH}M(CO)] (M = Mo, W). In contrast to known η-alkene molybdenum and tungsten compounds, the species presented here are easily isolated in the solid state. The tungsten compound [{η:κN-1-(CHN)CH}(η-CH)W(CO)][BF] is stable at room temperature, and its structure was unambiguously confirmed by X-ray diffraction. The reactivity of both propene complexes toward several monodentate donors was examined. In the case of dimethyl sulfide, ligand exchange takes place to afford [{η:κN-1-(CHN)CH}M(CO)(SMe)][BF] (M = Mo, W) while acetonitrile induces η→η haptotropic rearrangement to give [{η:κN-1-(CHN)CH}M(CO)(NCMe)][BF] (M = Mo, W).
我们在此报告了一类新型的钼和钨的丙烯-茚基混合配合物，它们通过强的N→M分子内配位作用得以稳定。配合物[{η:κN-1-(CHN)CH}(η-CH)M(CO)][BF]（M = Mo，W）是通过化合物[(η-CH){η-1-(CHN)CH}M(CO)]（M = Mo，W）中η-烯丙基配体的质子化反应以近乎定量的产率得到的。与已知的η-烯烃钼和钨化合物不同，此处呈现的这类物质很容易以固态形式分离出来。钨化合物[{η:κN-1-(CHN)CH}(η-CH)W(CO)][BF]在室温下是稳定的，其结构通过X射线衍射得到了明确证实。研究了这两种丙烯配合物对几种单齿供体的反应活性。对于二甲硫醚，会发生配体交换，生成[{η:κN-1-(CHN)CH}M(CO)(SMe)][BF]（M = Mo，W），而乙腈会引发η→η迁移重排，生成[{η:κN-1-(CHN)CH}M(CO)(NCMe)][BF]（M = Mo，W）。
