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Influence of 18-Crown‑6 Ether Coordination on the Catalytic Activity of Potassium and Calcium Diarylphosphinites in Hydrophosphorylation Reactions

The addition of 18-crown-6 ether (1,4,7,10,13,16-hexaoxacyclooctadecane) to tetranuclear [(thf)­K­(OPAryl2)]4 and [(thf)4Ca­(OPAryl2)2] yields the corresponding mononuclear complexes [(18C6)­K­(OPAryl2)] [Aryl = Ph (1a), Mes (1b)] and [(18C6)­Ca­(OPAryl2)2] [Aryl = Ph (2a), Mes (2b)]. The metathesis...

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Bibliographic Details
Published in:Inorganic chemistry 2017-08, Vol.56 (15), p.9255-9263
Main Authors: Härling, Stephan M, Krieck, Sven, Görls, Helmar, Westerhausen, Matthias
Format: Article
Language:English
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Summary:The addition of 18-crown-6 ether (1,4,7,10,13,16-hexaoxacyclooctadecane) to tetranuclear [(thf)­K­(OPAryl2)]4 and [(thf)4Ca­(OPAryl2)2] yields the corresponding mononuclear complexes [(18C6)­K­(OPAryl2)] [Aryl = Ph (1a), Mes (1b)] and [(18C6)­Ca­(OPAryl2)2] [Aryl = Ph (2a), Mes (2b)]. The metathesis reaction of [(thf)­K­(OPAryl2)]4 with CaI2 yields the calciate [K2Ca­(thf) x {OPMes2}4]. The addition of dimesitylphosphane oxide and crystallization from a hexane solution gives [K2Ca­{OPMes2}4{Mes2P­(O)­H}] (3). The complexes [(thf)­K­(OPMes2)]4, [(thf)4Ca­(OPMes2)2], 1b, 2b, and the calciate 3 are tested as catalysts in the hydrophosphorylation of isopropylisocyanate with dimesitylphosphane oxide, quantitatively yielding N-isopropyl­(dimesitylphosphoryl)­formamide. The potassium complexes are more efficient catalysts than the calcium congeners, and coordination of 18-crown-6 decelerates the catalytic conversion.
ISSN:0020-1669
1520-510X
DOI:10.1021/acs.inorgchem.7b01314