Sanderson Hugh J, Kociok-Köhn Gabriele, Hintermair Ulrich
Department of Chemistry, University of Bath, Claverton Down, Bath BA2 7AY, U.K.
Material and Chemical Characterisation Facility, University of Bath, Claverton Down, Bath BA2 7AY, U.K.
Inorg Chem. 2023 Oct 2;62(39):15983-15991. doi: 10.1021/acs.inorgchem.3c02087. Epub 2023 Sep 15.
The first magnesium pentalenide complexes have been synthesized deprotonative metalation of 1,3,4,6-tetraphenyldihydropentalene () with magnesium alkyls. Both the nature of the metalating agent and the reaction solvent influenced the structure of the resulting complexes, and an equilibrium between and was found to exist and investigated by NMR, XRD, and UV-vis spectroscopic techniques. Studies on the reactivity of with water, methyl iodide, and trimethylsilylchloride revealed that the unit undergoes electrophilic addition at 1,5-positions instead of 1,4-positions known for the unsubstituted pentalenide, , highlighting the electronic influence of the four aryl substituents on the pentalenide core. The ratio of / addition was found to be dependent on the size of the incoming electrophile, with methylation yielding a 60:40 mixture, while silylation yielded exclusively the -isomer.
首个戊搭烯化镁配合物已通过用烷基镁对1,3,4,6 - 四苯基二氢戊搭烯（ ）进行去质子金属化反应合成。金属化试剂的性质和反应溶剂都会影响所得配合物的结构，并且发现 和 之间存在平衡，并通过核磁共振（NMR）、X射线衍射（XRD）和紫外 - 可见光谱技术进行了研究。对 与水、碘甲烷和三甲基氯硅烷反应活性的研究表明， 单元在1,5 - 位发生亲电加成，而非未取代的戊搭烯化物 已知的1,4 - 位，这突出了四个芳基取代基对戊搭烯核的电子影响。发现 / 加成的比例取决于进入的亲电试剂的大小，甲基化产生60:40的混合物，而硅烷化仅产生 - 异构体。
