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Magnesium(I) Halide versus Magnesium Metal: Differences in Reaction Energy and Reactivity Monitored in Reduction Processes of P−Cl Bonds
Author(s) -
Arras Janet,
Kruczyński Tomasz,
Bresien Jonas,
Schulz Axel,
Schnöckel Hansgeorg
Publication year - 2019
Publication title -
angewandte chemie international edition
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 5.831
H-Index - 550
eISSN - 1521-3773
pISSN - 1433-7851
DOI - 10.1002/anie.201811053
Subject(s) - magnesium , chemistry , halide , metal , reagent , reactivity (psychology) , toluene , inorganic chemistry , chelation , molecule , medicinal chemistry , reaction mechanism , organic chemistry , catalysis , medicine , alternative medicine , pathology
Magnesium(I) halides (Mg I X; X=Cl, Br, I), as high temperature molecules, are trapped and finally stored at −80 °C in toluene/donor solutions. These solutions provide insights into the fundamental mechanism of reduction reactions using activated magnesium metal as a prototype for every base metal. The most important example of such a reaction is the preparation of Grignard reagents (RMgX). The details of this highly complex mechanism especially of intermediates between Mg metal and Mg II (RMgX) remain unknown until today. The same is true for the reaction of bulk magnesium with Group 15 halide compounds that give biradicaloid species. We investigate the reduction of P−Cl bonds with solutions of [Mg I Br(N n Bu 3 )] 2 ( 1 ). The phosphanes [ClP(μ‐NTer)] 2 ( 2 ) and (Me 3 Si) 2 N‐PCl 2 ( 3 ), were chosen as they had successfully been reduced by Mg metal before. Furthermore, reactions of both 1 and Mg metal are compared with an Mg I chelate complex L 1 Mg−MgL 1 containing a strong Mg−Mg σ‐bond.