Greño Maider, Pérez-Redondo Adrián, Torrijos José, Varela-Izquierdo Víctor, Yélamos Carlos
Departamento de Química Orgánica y Química Inorgánica, Instituto de Investigación Química "Andrés M. del Río" (IQAR), Universidad de Alcalá, 28805 Alcalá de Henares, Madrid, Spain.
Inorg Chem. 2024 Apr 15;63(15):6576-6588. doi: 10.1021/acs.inorgchem.3c02826. Epub 2024 Apr 3.
Half-sandwich zirconium(IV) and hafnium(IV) complexes with amidoborane and hydride ligands have been isolated in the stoichiometric reactions of mono(pentamethylcyclopentadienyl)metal alkyl and amido derivatives with the amine-boranes NHRBH (R = H, Me, HBu). Treatment of the tris(trimethylsilylmethyl) complexes [M(η-CMe)(CHSiMe)] with NHBH (3 equiv) gives the seven-coordinate species [M(η-CMe)(NHBH)] (M = Zr (), Hf ()) with three κ-NHBH ligands. The tris(neophyl) [M(η-CMe)(CHCMePh)] or tris(dimethylamido) [M(η-CMe)(NMe)] derivatives react with NHMeBH (≥3 equiv) to afford bis(dimethylamidoborane) hydride complexes [M(η-CMe)H(NMeBH)] (M = Zr (), Hf ()) via thermally unstable [M(η-CMe)(NMeBH)] species. The reaction of [M(η-CMe)(NMe)] and NHBuBH (≥4 equiv) affords analogous mixed amidoborane hydride derivatives [M(η-CMe)H(NHBuBH)(NMeBH)] (M = Zr (), Hf ()) with κ-NHBuBH and κ-NMeBH ligands. The addition of NHRBH (≥1 equiv) on the mono(dimethylamido) complexes [M(η-CMe)Cl(NMe)] in hexane leads to the precipitation of the ionic compounds [(NHR)BH][{M(η-CMe)Cl}(μ-H)] (R = Me, M = Zr (), Hf (); R = HBu, M = Zr (), Hf ()). Molecular hydride species [Cl(η-CMe)M(μ-Cl)(μ-H)M(η-CMe)Cl(NHBu)] (M = Zr (), Hf ()) could be isolated from mixtures of complexes [M(η-CMe)Cl(NMe)] and lower ratios of NHBuBH. The zirconium complex decomposes in solution to give the mononuclear -butylamido derivative [Zr(η-CMe)Cl(NHBu)] () along with other byproducts.
单（五甲基环戊二烯基）金属烷基和酰胺衍生物与胺硼烷NHRBH（R = H、Me、HBu）的化学计量反应中，分离得到了含有氨基硼烷和氢化物配体的半夹心锆（IV）和铪（IV）配合物。用NHBH（3当量）处理三（三甲基硅基甲基）配合物[M(η-CMe)(CHSiMe)]，得到具有三个κ-NHBH配体的七配位物种[M(η-CMe)(NHBH)]（M = Zr（），Hf（））。三（新戊基）[M(η-CMe)(CHCMePh)]或三（二甲基酰胺基）[M(η-CMe)(NMe)]衍生物与NHMeBH（≥3当量）反应，通过热不稳定的[M(η-CMe)(NMeBH)]物种生成双（二甲基氨基硼烷）氢化物配合物[M(η-CMe)H(NMeBH)]（M = Zr（），Hf（））。[M(η-CMe)(NMe)]与NHBuBH（≥4当量）反应，得到具有κ-NHBuBH和κ-NMeBH配体的类似混合氨基硼烷氢化物衍生物[M(η-CMe)H(NHBuBH)(NMeBH)]（M = Zr（），Hf（））。在己烷中，向单（二甲基酰胺基）配合物[M(η-CMe)Cl(NMe)]中加入NHRBH（≥1当量），会导致离子化合物[(NHR)BH][{M(η-CMe)Cl}(μ-H)]沉淀（R = Me，M = Zr（），Hf（）；R = HBu，M = Zr（），Hf（））。分子氢化物物种[Cl(η-CMe)M(μ-Cl)(μ-H)M(η-CMe)Cl(NHBu)]（M = Zr（），Hf（））可从配合物[M(η-CMe)Cl(NMe)]与较低比例的NHBuBH的混合物中分离得到。锆配合物 在溶液中分解，生成单核 -丁基酰胺基衍生物[Zr(η-CMe)Cl(NHBu)]（）以及其他副产物。
