Issue 42, 2021
From the journal:

Dalton Transactions

Oxidative addition, reduction and reductive coupling: the versatile reactivity of subvalent gallium cations†

Marcel Schorpp, ORCID logo *a   Razan Tamima  and  Ingo Krossing ORCID logo *a  

* Corresponding authors

a Institut für Anorganische und Analytische Chemie und Freiburger Materialforschungszentrum FMF, Albert-Ludwigs-Universität Freiburg, Albertstraße 21, 79104 Freiburg i. Br., Germany
E-mail: krossing@uni-freiburg.de

Abstract

Inspired by the successful oxidative addition of a P–H bond to univalent Ga[Al(ORF)4] that gives the unprecedented dicationic gallium hydride complex [H–Ga(PPh3)3][Al(ORF)4]2 (ORF = OC(CF3)3), the oxidative addition of E–Cl containing substrates was investigated. The reductive coupling of three PPh2Cl to the catenated phosphorus cation [P3Ph6]+ hinted towards a formal two-electron–three-halide reduction (2e−–3X− reduction). Similarly, from SbCl3, a cationic formal SbI compound and from RhCl3, [RhI(HMB)(COD)]+ and [RhI(COD)2]+ (HMB = C6Me6, COD = 1,5-cyclooctadiene) are formed as [Al(ORF)4]− salts when reacted with Ga+. Thus, Ga[Al(ORF)4] allows for a one-pot 2e−–3X− reduction with the concomitant introduction of a weakly coordinating anion (WCA).

Graphical abstract: Oxidative addition, reduction and reductive coupling: the versatile reactivity of subvalent gallium cations

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Article information

DOI
https://doi.org/10.1039/D1DT02682H
Article type
Paper
Submitted
11 Aug 2021
Accepted
08 Sep 2021
First published
13 Sep 2021

Dalton Trans., 2021,50, 15103-15110

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Oxidative addition, reduction and reductive coupling: the versatile reactivity of subvalent gallium cations

M. Schorpp, R. Tamim and I. Krossing, Dalton Trans., 2021, 50, 15103 DOI: 10.1039/D1DT02682H

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