Lebon Jakob, Barisic Damir, Maichle-Mössmer Cäcilia, Anwander Reiner
Institut für Anorganische Chemie, Eberhard Karls Universität Tübingen, Auf der Morgenstelle 18, 72076, Tübingen, Germany.
Chemistry. 2023 Nov 21;29(65):e202302846. doi: 10.1002/chem.202302846. Epub 2023 Oct 9.
The yttrium gallabenzene complex [(1-Me-3,5-tBu -C H Ga)(μ-Me)Y(2,4-dtbp)] is accessible from Y(GaMe ) and K(2,4-dtbp) via a tandem salt metathesis/methane elimination (2,4-dtbp=2,4-di-tert-butyl-pentadienyl). The pentadienyl ligand in [(1-Me-3,5-tBu -C H E)(μ-Me)Y(2,4-dtbp)] (E=Al, Ga) is easily displaced by salt metathesis with KC Me and KTp (Tp =tris(pyrazolyl-Me -3,5)borato) affording [(1-Me-3,5-tBu -C H E)(μ-Me)Y(Tp )] and [(1-Me-3,5-tBu -C H E)(μ-Me)Y(C Me )]. The yttrium center in [(1-Me-3,5-tBu -C H E)(μ-Me)Y(2,4-dtbp)] readily forms adducts with neutral Lewis bases like 4-DMAP (4-dimethylaminopyridine), PMe , DMPE (1,2-bis(dimethylphosphino)ethane), and DME (1,2-dimethoxyethane). In stark contrast, addition of TMEDA (N,N,N',N'-tetramethylethylenediamine) results in methyl/pentadienyl exchange between aluminum and yttrium resulting in [(1-(2,4-dtbp)-1-Me-3,5-tBu -C H Al)Y(Me)(tmeda)]. The bonding features of the newly synthesized complexes are analyzed by single-crystal X-ray diffraction (SCXRD) and heteronuclear ( Y, P) NMR spectroscopy.
钇镓苯配合物[(1-甲基-3,5-二叔丁基- C₅H₅Ga)(μ-甲基)Y(2,4-二叔丁基戊二烯基)]可通过串联盐复分解/甲烷消除反应由Y(GaMe₃)和K(2,4-二叔丁基戊二烯基)制得(2,4-二叔丁基戊二烯基=2,4-二叔丁基戊二烯基)。[(1-甲基-3,5-二叔丁基- C₅H₅E)(μ-甲基)Y(2,4-二叔丁基戊二烯基)](E = Al, Ga)中的戊二烯基配体可通过与KC₅Me₅和KTp（Tp =三(吡唑基-甲基-3,5)硼酸盐）进行盐复分解反应轻松置换，得到[(1-甲基-3,5-二叔丁基- C₅H₅E)(μ-甲基)Y(Tp₅)]和[(1-甲基-3,5-二叔丁基- C₅H₅E)(μ-甲基)Y(C₅Me₅)]。[(1-甲基-3,5-二叔丁基- C₅H₅E)(μ-甲基)Y(2,4-二叔丁基戊二烯基)]中的钇中心很容易与中性路易斯碱如4-DMAP（4-二甲氨基吡啶）、PMe₃、DMPE（1,2-双(二甲基膦基)乙烷）和DME（1,2-二甲氧基乙烷）形成加合物。与之形成鲜明对比的是，加入TMEDA（N,N,N',N'-四甲基乙二胺）会导致铝和钇之间发生甲基/戊二烯基交换，生成[(1-(2,4-二叔丁基戊二烯基)-1-甲基-3,5-二叔丁基- C₅H₅Al)Y(甲基)(tmeda)]。通过单晶X射线衍射（SCXRD）和异核(¹⁷Y, ³¹P) NMR光谱对新合成配合物的键合特征进行了分析。
