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Magnesium tetraorganyl derivatives of group 13 metals as intermediate products in the synthesis of group 13 metal alkyls and aryls
Author(s) -
Basiak Dariusz,
Wojciechowski Tomasz,
Rzepiński Patryk,
Dobrzycki Łukasz,
Wojewódzka Anna,
Monikowska Dorota,
ZygadłoMonikowska Ewa,
Ziemkowska Wanda
Publication year - 2020
Publication title -
applied organometallic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.53
H-Index - 71
eISSN - 1099-0739
pISSN - 0268-2605
DOI - 10.1002/aoc.5751
Subject(s) - chemistry , halide , alkyl , aryl , medicinal chemistry , magnesium , metal , metal halides , ionic bonding , stereochemistry , inorganic chemistry , organic chemistry , ion
Reactions of organomagnesium halides with group 13 metal halides lead to the formation of R 3 M type compounds (R = alkyl, aryl; M = Al, Ga, In) and are considered as the simplest methods of R 3 M compound syntheses. These seemingly simple reactions reveal a much more complex chemistry involving mixed magnesium‐group 13 metal compounds. To elucidate the reaction course of reactions of organomagnesium halides with group 13 metal halides, we have studied reactions of R 3 M with organomagnesium halides. The interaction of Et 3 M with R 1 MgX led to the formation of following products being mixtures of crystalline ionic complexes with the general composition of [Et 4‐n R 1 n M] − [XMg (thf) 5 ] + ·(thf): [Et 2.2 Al(CH=CH 2 ) 1.8 ] − [BrMg (thf) 5 ] + ·(thf) ( 1 ), [Et 3 Ga(CH=CH 2 )] − [BrMg (thf) 5 ] + ·(thf) ( 2 ), [Et 4 Al] − [BrMg (thf) 5 ] + ·(thf) ( 3 ), [Et 4 Ga] − [BrMg (thf) 5 ] + ·(thf) ( 4 ), [Et 2.9 Al(C 6 H 5 ) 1.1 ] − [BrMg (thf) 5 ] + ·(thf) ( 5 ), [Et 2.9 Ga(C 6 H 5 ) 1.1 ] − [BrMg (thf) 5 ] + ·(thf) ( 6 ), [Et 3.4 GaMe 0.6 ] − [IMg (thf) 5 ] + ·(thf) ( 7 ) and [Et 4 In] − [BrMg (thf) 5 ] + ·(thf) ( 8 ). A comparison of the production course of group 13 metal trialkyls R 3 M with a thermal decomposition of 1–8 products showed that reactions of MX 3 with RMgX (X = Br, I; R = alkyl, aryl) yield initially intermediate ionic compounds, which must then be thermally decomposed to obtain pure R 3 M compounds. If group 13 metal bromides and iodides, and alkyl (aryl)magnesium bromides and iodides in thf are used, only intermediate products with the [R 4 M] − [XMg (thf) 5 ] + ·(thf) structure are formed.