Potassium-Mediated Hydrophosphorylation of Heterocumulenes with Diarylphosphane Oxide and Sulfide

Stephan M Härling; Helmar Görls; Sven Krieck; Matthias Westerhausen

doi:10.1021/acs.inorgchem.6b01973

Potassium-Mediated Hydrophosphorylation of Heterocumulenes with Diarylphosphane Oxide and Sulfide

Inorg Chem. 2016 Oct 17;55(20):10741-10750. doi: 10.1021/acs.inorgchem.6b01973. Epub 2016 Sep 29.

Authors

Stephan M Härling¹, Helmar Görls¹, Sven Krieck¹, Matthias Westerhausen¹

Affiliation

¹ Institute of Inorganic and Analytical Chemistry, Friedrich Schiller University Jena , Humboldtstrasse 8, D-07743 Jena, Germany.

PMID: 27685469
DOI: 10.1021/acs.inorgchem.6b01973

Abstract

The preparation of the hydrophosphorylation catalysts succeeds via the metalation of dimesitylphosphane oxide and diphenylphosphane sulfide with potassium hydride in ethereal solvents such as tetrahydropyran (THP) and tetrahydrofuran (THF) yielding the tetramers [(thp)K(OPMes₂)]₄ (1a) and [(thf)₃{K(OPMes₂)}₄] (1b) as well as [(thp)KSPPh₂]_∞ (2) with a strand-like structure in the crystalline state. In ethereal solution these complexes very slowly degrade into KPAr₂ and KE₂PAr₂ (E = O, S). The catalytic conversion of iPr-N═C═E' (E' = O, S) and of R-N═C═N-R (R = iPr, cHex) to the addition products Ar2P(E)-C(=E')-NHR (Ar = Ph, Mes; E = O, S; E' = O, S, NR) was studied in the presence of catalytic amounts of Ar₂PEK (Ar = Ph, Mes; E = O, S). Steric hindrance prevents the addition of dimesitylphosphane oxide to N,N'-diisopropylcarbodiimide, whereas diphenylphosphane oxide and sulfide smoothly add to iPr-N═C═N-iPr yielding Ph₂P(E)-C(═N-iPr)-NHiPr (E = O, S).