Ghana Priyabrata, Schrader Sebastian, Rajeshkumar Thayalan, Spaniol Thomas P, Englert Ulli, Maron Laurent, Okuda Jun
Institute of Inorganic Chemistry, RWTH Aachen University, Landoltweg 1, 52056, Aachen, Germany.
Université de Toulouse et CNRS, INSA, UPS, UMR 5215, LPCNO, 135 Avenue de Rangueil, F-31077, Toulouse, France.
Angew Chem Int Ed Engl. 2021 Jun 14;60(25):14179-14187. doi: 10.1002/anie.202103755. Epub 2021 May 7.
A series of hafnium complexes with a reduced arene of the general formula [K(L)][Hf(Xy-N N)(arene)] (Xy-N N={(3,5-Me C H )NCH CH } N , L=THF, 18-crown-6; arene=C H , C H ) mimic the chemistry of hafnium in its formal oxidation state +II. All compounds were obtained upon reduction of the chlorido complex [HfCl(Xy-N N)(thf)] with two equivalents of potassium naphthalenide or anthracenide. The reducing nature and the basicity of the reduced anthracene ligand were explored in the reaction of benzonitrile and azobenzene, and by deprotonation of tert-butylacetylene, respectively. The reduction of benzonitrile provides an initial double nitrile insertion product under kinetic control that rearranges after extrusion of one of the inserted nitriles to a hafnium imido complex as the thermodynamic product. The reduction of azobenzene resulted in a diphenylhydrazido(2-) complex. Treatment of terminal alkynes with the anthracene or diphenylhydrazido(2-) complex led to the selective protonation of the corresponding dianionic ligand.
一系列通式为[K(L)][Hf(Xy-N N)(芳烃)]（Xy-N N ={(3,5-Me₂C₆H₃)NCH₂CH₂}₂N²⁻，L = THF，18-冠-6；芳烃 = C₆H₆，C₆H₄Me₂）且芳烃被还原的铪配合物模拟了处于形式氧化态+II的铪的化学性质。所有化合物都是通过用两当量的萘基钾或蒽基钾还原氯代配合物[HfCl(Xy-N N)(thf)]得到的。分别在苯甲腈和偶氮苯的反应中以及通过叔丁基乙炔的去质子化反应，研究了还原蒽配体的还原性和碱性。苯甲腈的还原在动力学控制下提供了一种初始的双腈插入产物，在挤出其中一个插入的腈后重排为铪亚胺配合物作为热力学产物。偶氮苯的还原产生了一种二苯基肼基(2-)配合物。用蒽或二苯基肼基(2-)配合物处理末端炔烃导致相应双阴离子配体的选择性质子化。
