Potassium-Mediated Hydrophosphorylation of Heterocumulenes with Diarylphosphane Oxide and Sulfide.
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 KPAr2and 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).
Institute of Inorganic and Analytical Chemistry, Friedrich Schiller University Jena , Humboldtstrasse 8, D-07743 Jena, Germany.
Stephan M
SM
Härling
Institute of Inorganic and Analytical Chemistry, Friedrich Schiller University Jena , Humboldtstrasse 8, D-07743 Jena, Germany.
Helmar
H
Görls
Institute of Inorganic and Analytical Chemistry, Friedrich Schiller University Jena , Humboldtstrasse 8, D-07743 Jena, Germany.
Sven
S
Krieck
Institute of Inorganic and Analytical Chemistry, Friedrich Schiller University Jena , Humboldtstrasse 8, D-07743 Jena, Germany.
Matthias
M
Westerhausen