Hexaphenyl carbodiphosphorane adducts of heavier group 15 element trichlorides: syntheses, properties and reactivities. Issue 29 (1st July 2019)

• Record Type: Journal Article
• Authors: Münzer, Jörn E.; Kneusels, Nis-Julian H.; Weinert, Bastian; Neumüller, Bernhard; Kuzu, Istemi
• Is Part Of: Dalton transactions. Volume 48:Issue 29(2019)
• Page Start: 11076
• Page End: 11085
• Publication Date: 2019-07-01
• Subjects: Chemistry, Inorganic -- Periodicals; Chemistry, Physical and theoretical -- Periodicals; Chemistry, Inorganic -- Periodicals; 546.05
• DOI: 10.1039/c9dt01784d
• Languages: English
• ISSNs: 1477-9226

Abstract

Abstract : Herein, we present the series of hexaphenyl carbodiphosphorane (CDP Ph ) adducts of heavier group 15 trichlorides ECl3 (E = P-Bi). Abstract : Herein, we present a series of hexaphenyl carbodiphosphorane (CDP Ph ) adducts of heavier group 15 trichlorides ECl3 (E = P-Bi). The reaction with PCl3 yields the known salt [CDP Ph –PCl2 ][Cl] ([1 ][Cl]), the heavier element trichlorides ECl3 (E = Sb (4 ), Bi (5 )) give the neutral adducts CDP Ph –ECl3 which were characterised crystallographically and spectroscopically. The reaction of CDP Ph with AsCl3 does not yield CDP Ph –AsCl3 (2 ), but in the presence of GaCl3 the corresponding salt [CDP Ph –AsCl2 ][GaCl4 ] ([3 ][GaCl4 ]) is formed. DFT (density functional theory) calculations were carried out to examine the molecular frontier orbitals in1 + –5 . Additional reactivity studies revealed an intramolecular electrophilic aromatic substitution (SE Ar) in1 +, which represents an excellent starting point for further selective C–P bond formation reactions.