Magnesium tetraorganyl derivatives of group 13 metals as intermediate products in the synthesis of group 13 metal alkyls and aryls

Dariusz Basiak , Tomasz Wojciechowski , Patryk Rzepiński , Łukasz Dobrzycki , Anna Wojewódzka , Dorota Monikowska , Ewa Zygadło-Monikowska , Wanda Ziemkowska

Abstract

Reactions of organomagnesium halides with group 13 metal halides lead to the formation of R3M type compounds (R = alkyl, aryl; M = Al, Ga, In) and are considered as the simplest methods of R3M 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 R3M with organomagnesium halides. The interaction of Et3M with R1MgX led to the formation of following products being mixtures of crystalline ionic complexes with the general composition of [Et4-nR1nM][XMg (thf)5]+·(thf): [Et2.2Al(CH=CH2)1.8][BrMg (thf)5]+·(thf) (1), [Et3Ga(CH=CH2)][BrMg (thf)5]+·(thf) (2), [Et4Al][BrMg (thf)5]+·(thf) (3), [Et4Ga][BrMg (thf)5]+·(thf) (4), [Et2.9Al(C6H5)1.1][BrMg (thf)5]+·(thf) (5), [Et2.9Ga(C6H5)1.1][BrMg (thf)5]+·(thf) (6), [Et3.4GaMe0.6][IMg (thf)5]+·(thf) (7) and [Et4In][BrMg (thf)5]+·(thf) (8). A comparison of the production course of group 13 metal trialkyls R3M with a thermal decomposition of 1–8 products showed that reactions of MX3 with RMgX (X = Br, I; R = alkyl, aryl) yield initially intermediate ionic compounds, which must then be thermally decomposed to obtain pure R3M compounds. If group 13 metal bromides and iodides, and alkyl (aryl)magnesium bromides and iodides in thf are used, only intermediate products with the [R4M][XMg (thf)5]+·(thf) structure are formed.

Author Dariusz Basiak (FC / DCOC)
Dariusz Basiak,,
- Department Of Catalysis And Organometallic Chemistry
, Tomasz Wojciechowski (FC / DCOC)
Tomasz Wojciechowski,,
- Department Of Catalysis And Organometallic Chemistry
, Patryk Rzepiński - Faculty of Chemistry (WChUW) [University of Warsaw (UW)]
Patryk Rzepiński,,
-
, Łukasz Dobrzycki - Faculty of Chemistry (WChUW) [University of Warsaw (UW)]
Łukasz Dobrzycki,,
-
, Anna Wojewódzka (FC / DCOC)
Anna Wojewódzka,,
- Department Of Catalysis And Organometallic Chemistry
, Dorota Monikowska (FC / CPCT)
Dorota Monikowska,,
- Chair Of Polymer Chemistry And Technology
, Ewa Zygadło-Monikowska (FC / CPCT)
Ewa Zygadło-Monikowska,,
- Chair Of Polymer Chemistry And Technology
, Wanda Ziemkowska (FC / DCOC)
Wanda Ziemkowska,,
- Department Of Catalysis And Organometallic Chemistry
Journal seriesApplied Organometallic Chemistry, ISSN 0268-2605, e-ISSN 1099-0739, [1099-0739]
Issue year2020
Pages1-12
Publication size in sheets0.55
Keywords in EnglishGrignard reagents, group 13 metal trialkyls and –aryls, intermediate products, ionic crystalline “ate” compounds
ASJC Classification1600 General Chemistry; 1604 Inorganic Chemistry
DOIDOI:10.1002/aoc.5751
URL https://onlinelibrary.wiley.com/doi/full/10.1002/aoc.5751?af=R
Languageen angielski
File
aoc.5751.pdf 1.82 MB
Score (nominal)100
Score sourcejournalList
ScoreMinisterial score = 100.0, 30-07-2020, ArticleFromJournal
Publication indicators Scopus Citations = 0; Scopus SNIP (Source Normalised Impact per Paper): 2018 = 0.676; WoS Impact Factor: 2018 = 3.259 (2) - 2018=3.013 (5)
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