Nesterov Vitaly, Baierl Ramona, Hanusch Franziska, Ferao Arturo Espinosa, Inoue Shigeyoshi
Department of Chemistry, WACKER-Institute of Silicon Chemistry and Catalysis Research Center , Technische Universität München , Lichtenbergstraße 4 , 85748 Garching bei München , Germany.
Departamento de Química Orgánica, Facultad de Química , Universidad de Murcia , Campus de Espinardo, 30100 Murcia , Spain.
J Am Chem Soc. 2019 Sep 18;141(37):14576-14580. doi: 10.1021/jacs.9b08741. Epub 2019 Sep 10.
The synthesis of stable heavier analogues of nitriles as monomeric tetrylene-phosphinidenes TerEP(IDipp) (E = Ge, Sn; Ter = 2,6-MesCH, IDipp = C([N-(2,6-PrCH)CH]) was achieved by taking advantage of NHC (N-heterocyclic carbene, here IDipp) coordination to the low-valent phosphorus center. Multiple bonding character of the E-P bonds was examined experimentally and computationally. Both germanium and tin compounds undergo [2+2] cycloaddition with diphenylketene, whereas reaction of the tin derivative with (pentafluorophenyl)borane provided unique "push-pull" phosphastannene (Ter)(Ar)Sn = P(IDipp) (Ar = CF[B(F)(CF)]). Going further, we demonstrated the potential of tetrylene-phosphinidene complexes in catalytic hydroboration of carbonyl compounds.
通过利用氮杂环卡宾（NHC，此处为IDipp）与低价磷中心的配位作用，实现了腈类稳定较重类似物作为单体四元环磷烯TerEP(IDipp)（E = Ge，Sn；Ter = 2,6-MesCH，IDipp = C([N-(2,6-PrCH)CH])的合成。通过实验和计算研究了E-P键的多重键合特性。锗和锡化合物都能与二苯基乙烯酮发生[2+2]环加成反应，而锡衍生物与（五氟苯基）硼烷的反应则提供了独特的“推-拉”磷锡烯（Ter）(Ar)Sn = P(IDipp)（Ar = CF[B(F)(CF)]）。进一步地，我们证明了四元环磷烯配合物在催化羰基化合物硼氢化反应中的潜力。
