N-Heterocyclic Carbene-Stabilized Germanium and Tin Analogues of Heavier Nitriles: Synthesis, Reactivity, and Catalytic Application

Vitaly Nesterov; Ramona Baierl; Franziska Hanusch; Arturo Espinosa Ferao; Shigeyoshi Inoue

doi:10.1021/jacs.9b08741

N-Heterocyclic Carbene-Stabilized Germanium and Tin Analogues of Heavier Nitriles: Synthesis, Reactivity, and Catalytic Application

J Am Chem Soc. 2019 Sep 18;141(37):14576-14580. doi: 10.1021/jacs.9b08741. Epub 2019 Sep 10.

Authors

Vitaly Nesterov¹, Ramona Baierl¹, Franziska Hanusch¹, Arturo Espinosa Ferao², Shigeyoshi Inoue¹

Affiliations

¹ Department of Chemistry, WACKER-Institute of Silicon Chemistry and Catalysis Research Center , Technische Universität München , Lichtenbergstraße 4 , 85748 Garching bei München , Germany.
² Departamento de Química Orgánica, Facultad de Química , Universidad de Murcia , Campus de Espinardo, 30100 Murcia , Spain.

PMID: 31476856
DOI: 10.1021/jacs.9b08741

Abstract

The synthesis of stable heavier analogues of nitriles as monomeric tetrylene-phosphinidenes ^MesTerEP(IDipp) (E = Ge, Sn; ^MesTer = 2,6-Mes₂C₆H₃, IDipp = C([N-(2,6-iPr₂C₆H₄)CH]₂) 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 tris(pentafluorophenyl)borane provided unique "push-pull" phosphastannene (^MesTer)(Ar)Sn = P(IDipp) (Ar = C₆F₄[B(F)(C₆F₅)₂]). Going further, we demonstrated the potential of tetrylene-phosphinidene complexes in catalytic hydroboration of carbonyl compounds.