Synthesis, Structure, and Stability of Lithium Arylphosphanidyl‐diarylphosphane Oxide. Issue 13 (4th February 2020)

• Record Type: Journal Article
• Authors: Bevern, Damian; Görls, Helmar; Krieck, Sven; Westerhausen, Matthias
• Is Part Of: Zeitschrift für anorganische und allgemeine Chemie. Volume 646:Issue 13(2020)
• Page Start: 948
• Page End: 958
• Publication Date: 2020-02-04
• Subjects: Phosphanides -- Lithium -- Potassium -- Phosphanidylphosphane oxides -- Mechanistic study; Chemistry, Inorganic -- Periodicals; Chemistry -- Periodicals; 540
• DOI: 10.1002/zaac.201900327
• Languages: English
• ISSNs: 0044-2313

Abstract

Abstract : The reaction of LiP(H)Tipp (2a ) and KP(H)Tipp (2b, Tipp = C6 H2 ‐2, 4, 6‐ i Pr3 ), which are accessible via metalation of Tipp‐PH2 (1 ), with bis(4‐ tert ‐butylphenyl)phosphinic chloride yields Tipp‐P=P(OM)Ar2 [M = Li (3a ) and K (3b )]. These complexes show characteristic chemical 31 P shifts and large 1 JPP coupling constants. These compounds degrade with elimination of the phosphinidene Tipp‐P: and the alkali metal diarylphosphinites M–O–PAr2 [M = Li (4a ) and K (4b )]. The phosphinidene forms secondary degradation products (like the meso and R, R/S, S ‐isomers of diphosphane Tipp‐P(H)–P(H)Tipp (5 ) via insertion into a P–H bond of newly formed Tipp‐PH2 ), whereas the crystallization of [Tipp‐P=P(OLi)Ar2 · LiOPAr2 · LiCl· 2Et2 O]2 (i.e. [3a·4a· LiCl· 2Et2 O]2 ) succeeds from diethyl ether. The metathesis reactions of LiP(Si i Pr3 )Tipp and LiP(Si i Pr3 )Mes (Mes = C6 H2 ‐2, 4, 6‐Me3 ) with Ar2 P(O)Cl yield Ar*‐P=P(OSi i Pr3 )Ar2 (Ar* = Mes, Tipp) which degrade to Ar2 POSi i Pr3 and other secondary products. Abstract :