Hexaphenyl carbodiphosphorane adducts of heavier group 15 element trichlorides: syntheses, properties and reactivities

• Published in: Dalton transactions : an international journal of inorganic chemistry Vol. 48; no. 29; pp. 1176 - 1185
• Main Authors: Münzer, Jörn E, Kneusels, Nis-Julian H, Weinert, Bastian, Neumüller, Bernhard, Kuzu, Istemi
• Format: Journal Article
• Language: English
• Published: England Royal Society of Chemistry 07.08.2019
• Subjects: Adducts; Antimony; Bismuth; Crystallography; Density functional theory; Gallium chloride; NMR; Nuclear magnetic resonance; Substitution reactions
• ISSN: 1477-9226; 1477-9234
• DOI: 10.1039/c9dt01784d

Herein, we present a series of hexaphenyl carbodiphosphorane (CDP Ph ) adducts of heavier group 15 trichlorides ECl 3 (E = P-Bi). The reaction with PCl 3 yields the known salt [CDP Ph -PCl 2 ][Cl] ([ 1 ][Cl]), the heavier element trichlorides ECl 3 (E = Sb ( 4 ), Bi ( 5 )) give the neutral adducts CDP Ph -ECl 3 which were characterised crystallographically and spectroscopically. The reaction of CDP Ph with AsCl 3 does not yield CDP Ph -AsCl 3 ( 2 ), but in the presence of GaCl 3 the corresponding salt [CDP Ph -AsCl 2 ][GaCl 4 ] ([ 3 ][GaCl 4 ]) is formed. DFT (density functional theory) calculations were carried out to examine the molecular frontier orbitals in 1 + -5 . Additional reactivity studies revealed an intramolecular electrophilic aromatic substitution (S E Ar) in 1 + , which represents an excellent starting point for further selective C-P bond formation reactions. Herein, we present the series of hexaphenyl carbodiphosphorane (CDP Ph ) adducts of heavier group 15 trichlorides ECl 3 (E = P-Bi).