A Three‐Membered Cyclic Phosphasilene. Issue 7 (18th January 2019)

• Record Type: Journal Article
• Authors: Heider, Yannic; Willmes, Philipp; Mühlhausen, Daniel; Klemmer, Lukas; Zimmer, Michael; Huch, Volker; Scheschkewitz, David
• Is Part Of: Angewandte Chemie international edition. Volume 58:Issue 7(2019)
• Page Start: 1939
• Page End: 1944
• Publication Date: 2019-01-18
• Subjects: coordination chemistry -- heavier multiple bonds -- phosphorus -- silicon -- small rings; Chemistry -- Periodicals; 540
• DOI: 10.1002/anie.201811944
• Languages: English
• ISSNs: 1433-7851

Abstract

Abstract: Small unsaturated phosphacycles are versatile reagents owing to their strain and the added functionality of the double bond and the phosphorus lone pair. Herein we report the synthesis and isolation of the smallest possible cyclic phosphasilene as a stable adduct with an N‐heterocyclic carbene (NHC). First reactivity studies show a) that the PSi2 ring is a competent ligand to the Fe(CO)4 fragment via the phosphorus lone pair and b) that the abstraction of the NHC by BPh3 results in the rapid head‐to‐head or head‐to‐tail dimerization of the PSi2 unit. The relatively facile NHC cleavage indicates that the P=Si double bond is available for further manipulation. Abstract : The smallest cyclic Si=P species : A phosphorus(I) cation was used as a precursor for the synthesis of the first three‐membered cyclic phosphasilene. The highly strained ring compound can be coordinated to a transition metal through the ylidic phosphorus center or "clicked" with itself to give two cluster‐like Si4 P2 isomers.