Institut für Anorganische Chemie, Universität Regensburg, 93040, Regensburg, Germany.
Institute of Chemistry, St. Petersburg State University, Universitetskaya emb. 7/9, 199037, St. Petersburg, Russia.
Chemistry. 2019 Oct 28;25(60):13714-13718. doi: 10.1002/chem.201903887. Epub 2019 Oct 4.
The pnictogenyl Group 13 compounds (Dipp Nacnac)M[E(SiMe ) ]Cl and (Dipp Nacnac)M(EH ) (Dipp Nacnac=HC[C(Me)N(Ar)] , Ar: Dipp=2,6-iPr C H ; M=Al, Ga, In; E=P, As) were successfully synthesized. The salt metathesis between (Dipp Nacnac)MCl and LiE(SiMe ) only led to monosubstituted compounds (Dipp Nacnac)M[E(SiMe ) ]Cl [E=P, M=Ga(1), In (2); E=As, M=Ga (3), In (4)], regardless of the stoichiometric ratios used. In contrast to the steric effect of the SiMe groups in 1-4, the reactions of the corresponding halides with LiPH ⋅DME (or KAsH ) facilely yielded the dipnictogenide compounds (Dipp Nacnac)M(EH ) (E=P, M=Al (5), Ga (6), In (7); E=As, M=Al (8), Ga (9)), avoiding the use of flammable and toxic PH and AsH for their synthesis. The compounds 5-9 are the first examples of monomeric Group 13 diphosphanides and diarsanides in which the metal center is bound to two terminal PH and AsH groups, respectively. In contrast to the successful synthesis of the indium diphosphanide (Dipp Nacnac)In(PH ) , the reaction of (Dipp Nacnac)InCl with KAsH led to an indium mirror due to the instability of the target product.
第 13 族 pnictogenyl 化合物（Dipp Nacnac）M[E（SiMe ）]Cl 和（Dipp Nacnac）M（EH）（Dipp Nacnac=HC[C(Me)N(Ar)]，Ar：Dipp=2,6-iPr 2 C 6 H 3 ；M=Al、Ga、In；E=P、As）成功合成。（Dipp Nacnac）MCl 与 LiE（SiMe ）之间的盐复分解反应仅导致单取代化合物（Dipp Nacnac）M[E（SiMe ）]Cl [E=P，M=Ga（1），In（2）；E=As，M=Ga（3），In（4）]，无论使用的化学计量比如何。与 1-4 中 SiMe 基团的空间位阻效应相反，相应卤化物与 LiPH ⋅DME（或 KAsH）的反应容易得到双磷化物化合物（Dipp Nacnac）M（EH）（E=P，M=Al（5），Ga（6），In（7）；E=As，M=Al（8），Ga（9）），避免了使用易燃和有毒的 PH 和 AsH 进行合成。化合物 5-9 是首例单核第 13 族双膦化物和二砷化物，其中金属中心分别与两个末端 PH 和 AsH 基团键合。与成功合成的单体 indium 双膦化物（Dipp Nacnac）In（PH）不同，（Dipp Nacnac）InCl 与 KAsH 的反应由于目标产物不稳定而导致生成 indium 镜。
