Anga Srinivas, Acharya Joydev, Chandrasekhar Vadapalli
Tata Institute of Fundamental Research Hyderabad, Gopanpally 500046, Hyderabad, India.
Department of Chemistry, IIT Kanpur, Kanpur 208016, India.
J Org Chem. 2021 Feb 5;86(3):2224-2234. doi: 10.1021/acs.joc.0c02383. Epub 2020 Dec 2.
An imino-phosphanamide ligand, [NHIP(Ph)NH-2,6-PrCH] (), containing two different -substituents was prepared by the direct reaction of the lithium salt of -heterocyclic imine (NHI) with phenylchloro-2,6-diisopropylphenyl phosphanamine, PhP(Cl)NH-2,6-Pr-CH. Reaction of with Y(N(SiMe)) afforded the heteroleptic complex, [{L}Y(N(SiMe))] (), by elimination of HN(SiMe). Compound was characterized by multinuclear NMR and X-ray crystallography. In the complex, the Y(III) center was found to be tetracoordinate in a distorted tetrahedral geometry. The ligand, imino-phosphanamidinate, [L], functions in a chelating manner, and its coordination to Y(III) results in a distorted 4-membered YPN ring. As a proof of principle of its activity, was used as a precatalyst for the hydroboration of various aldehydes and ketones using HBpin as the hydrogen source. The hydroboration reaction was rapid and clean even with low catalyst loadings (0.01-0.1 mol %). In addition, a very good functional group tolerance was observed in these reactions.
通过杂环亚胺（NHI）的锂盐与苯基氯-2,6-二异丙基苯基膦胺，即PhP(Cl)NH-2,6-Pr-CH直接反应，制备了一种含有两个不同取代基的亚氨基膦酰胺配体，[NHIP(Ph)NH-2,6-PrCH]（ ）。 将 与Y(N(SiMe) )反应，通过消除HN(SiMe)得到杂配体配合物[{L}Y(N(SiMe) )]（ ）。 化合物 通过多核NMR和X射线晶体学进行了表征。 在该配合物中，发现Y(III)中心以扭曲的四面体几何构型呈四配位。 亚氨基膦脒配体[L]以螯合方式起作用，其与Y(III)的配位导致形成一个扭曲的四元YPN环。 作为其活性原理的证明， 使用HBpin作为氢源，用作各种醛和酮硼氢化反应的预催化剂。 即使在低催化剂负载量（0.01 - 0.1 mol%）下，硼氢化反应也迅速且干净。 此外，在这些反应中观察到了非常好的官能团耐受性。
