Synthesis and redox activity of carbene-coordinated group 13 metal radicals

Electrophilic AlIII species have long dominated the aluminum reactivity towards arenes. Recently, nucleophilic low‐valent AlI aluminyl anions have showcased oxidative additions towards arenes C−C and/or C−H bonds. Herein, we communicate compelling evidence of an AlII radical addition reaction to the benzene ring. The electron reduction of a ligand stabilized precursor with KC8 in benzene furnishes a double addition to the benzene ring instead of a C−H bond activation, producing the corresponding cyclohexa‐1,3(orl,4)‐dienes as Birch‐type reduction product. X‐ray crystallographic analysis, EPR spectroscopy, and DFT results suggest this reactivity proceeds through a stable AlII radical intermediate, whose stability is a consequence of a rigid scaffold in combination with strong steric protection.

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Evidence of Al^IIRadical Addition to Benzene

Mandal

Demirer

Sergeieva

et al. 2023

Angewandte Chemie

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Evidence of Al^IIRadical Addition to Benzene

et al. 2023

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NHC‐Stabilised Parent Tripentelyltrielanes

Szlosek

Weinhart

Baláȥs

et al. 2023

Chemistry A European J

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A missing family of the extremely air sensitive tripentelyltrielanes was discovered. Their stabilisation was achieved by using the bulky NHC IDipp (NHC=N‐heterocyclic carbene, IDipp=1,3‐bis(2,6‐diisopropylphenyl)‐imidazolin‐2‐ylidene). The tripentelylgallanes and tripentelylalanes IDipp ⋅ Ga(PH2)3 (1 a), IDipp ⋅ Ga(AsH2)3 (1 b), IDipp ⋅ Al(PH2)3 (2 a) and IDipp ⋅ Al(AsH2)3 (2 b) were synthesised by salt metathesis of IDipp ⋅ ECl3 (E=Al, Ga, In) with alkali metal pnictogenides such as NaPH2/LiPH2 ⋅ DME and KAsH2, respectively. Moreover, the detection of the first NHC‐stabilised tripentelylindiumane IDipp ⋅ In(PH2)3 (3) was possible by multinuclear NMR spectroscopy. Initial investigations of the coordination ability of these compounds resulted in the successful isolation of the coordination compound [IDipp ⋅ Ga(PH2)2(μ3‐PH2{HgC6F4}3)] (4) by reaction of 1 a with (HgC6F4)3. The compounds were characterised by multinuclear NMR spectroscopy as well as single crystal X‐ray diffraction studies. Supporting computational studies highlight the electronic features of the products.

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Synthesis and redox activity of carbene-coordinated group 13 metal radicals

Abstract: Carbenes are known to stabilize main group element compounds with unusual electronic properties. Herein, we report the synthesis of carbene-stabilized group 13 metal radicals (cAAC)MX2(IPr) (M = Al, X =...

Cited by 6 publications

References 59 publications

Evidence of Al^IIRadical Addition to Benzene

Evidence of Al^IIRadical Addition to Benzene

Evidence of Al^IIRadical Addition to Benzene

NHC‐Stabilised Parent Tripentelyltrielanes

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Synthesis and redox activity of carbene-coordinated group 13 metal radicals

Abstract: Carbenes are known to stabilize main group element compounds with unusual electronic properties. Herein, we report the synthesis of carbene-stabilized group 13 metal radicals (cAAC)MX2(IPr) (M = Al, X =...

Cited by 6 publications

References 59 publications

Evidence of AlIIRadical Addition to Benzene

Evidence of AlIIRadical Addition to Benzene

Evidence of AlIIRadical Addition to Benzene

NHC‐Stabilised Parent Tripentelyltrielanes

Contact Info

Product

Resources

About

Evidence of Al^IIRadical Addition to Benzene

Evidence of Al^IIRadical Addition to Benzene

Evidence of Al^IIRadical Addition to Benzene