Functionalization of Pentaphosphorus Cations by Complexation.

ABSTRACT: The chemistry of polyphosphorus cations has rapidly developed in recent years, but their coordination behavior has remained mostly unexplored. Herein, we describe the reactivity of [P₅ R₂ ]⁺ cations with cyclopentadienyl metal complexes. The reaction of [Cp^Ar Fe(?-Br)]₂ (Cp^Ar =C₅ (C₆ H₄ -4-Et)₅ ) with [P₅ R₂ ][GaCl₄ ] (R=iPr and 2,4,6-Me₃ C₆ H₂ (Mes)) afforded bicyclo[1.1.0]pentaphosphanes (1-R, R=iPr and Mes), showing an unsymmetric "butterfly" structure. The same products 1-R were formed from K[Cp^Ar ] and [P₅ R₂ ][GaCl₄ ]. The cationic complexes [Cp^Ar Co(?⁴ -P₅ R₂ )][GaCl₄ ] (2-R[GaCl₄ ], R=iPr and Cy) and [(Cp^Ar Ni)₂ (?^3:3 -P₅ R₂ )][GaCl₄ ] (3-R[GaCl₄ ]) were obtained from [P₅ R₂ ][GaCl₄ ] and [Cp^Ar M(?-Br)]₂ (M=Co and Ni) as well as by using low-valent "Cp^Ar M^I " sources. Anion metathesis of 2-R[GaCl₄ ] and 3-R[GaCl₄ ] was achieved with Na[BArF₂₄ ]. The P₅ framework of the resulting salts 2-R[BArF₂₄ ] can be further functionalized with nucleophiles. Thus reactions with [Et₄ N]X (X=CN and Cl) give unprecedented cyano- and chloro-functionalized complexes, while organo-functionalization was achieved with CyMgCl.

SUBMITTER: Adhikari AK 

PROVIDER: S-EPMC6916545 | biostudies-literature | 2019 Dec

REPOSITORIES: biostudies-literature