Synthesis and characterisation of tetramethylpiperidinyloxide (TEMPO) complexes of group 13 metal hydrides

Jones, Cameron; Rose, Richard P.

doi:10.1039/b702641b

Cited by 32 publications

(18 citation statements)

References 20 publications

(14 reference statements)

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“…It was found that [MH 3 (quin)] (quin = quinuclidine, M = Al or Ga) reacts with TEMPO (1 equiv), probably via the corresponding metal trihydride/ TEMPO adduct, by a formal homolytic substitution at the Group 13 metal to generate quinuclidine-complexed TEM-POMH 2 along with dihydrogen. [151] Moreover, the reaction of [AlH 3 (quin)] with two equivalents of TEMPO provided [(TEMPO) 2 AlH(quin)]. In analogy to some Group 13 metal hydrides, aryl zinc hydride dimer 55 reacted with TEMPO at elevated temperature to generate aryl zinc alkoxide 56, probably through an associative mechanism, as also suggested above for the Group 13 metal hydrides (Scheme 25).…”

Section: H Abstraction By Nitroxidesmentioning

confidence: 77%

Nitroxides: Applications in Synthesis and in Polymer Chemistry

2011

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This Review describes the application of nitroxides to synthesis and polymer chemistry. The synthesis and physical properties of nitroxides are discussed first. The largest section focuses on their application as stoichiometric and catalytic oxidants in organic synthesis. The oxidation of alcohols and carbanions, as well as oxidative C-C bond-forming reactions are presented along with other typical oxidative transformations. A section is also dedicated to the extensive use of nitroxides as trapping reagents for C-centered radicals in radical chemistry. Alkoxyamines derived from nitroxides are shown to be highly useful precursors of C-centered radicals in synthesis and also in polymer chemistry. The last section discusses the basics of nitroxide-mediated radical polymerization (NMP) and also highlights new developments in the synthesis of complex polymer architectures.

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Section: H Abstraction By Nitroxidesmentioning

confidence: 77%

Nitroxides: Applications in Synthesis and in Polymer Chemistry

2011

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“…Several gallium complexes incorporating hydroxyl amine ligands have been structurally characterized, and the Ga-O and N-O distances observed for 1 compare well to their metrics. As representative examples, the Ga-O bond length in the (Me 2 GaONMe 2 ) 2 complex is 1.886(2) Å and the N-O distance was 1.435(3) Å [28] while the analogous distances in the GaH 2 (quinuclidine)(TEMPO) (TEMPO = tetramethylpiperidinyloxide) complex are 1.850(5) and 1.447(8) Å, respectively [29]. Finally, the series of bis(hydroxylamine) gallium complexes prepared by the Mitzel group have an average Ga-O distance of 1.91 Å and average N-O distance of 1.44 Å [30,31].…”

Section: Solid-state Theoreticalmentioning

confidence: 99%

Synthesis and Characterization of (pyNO−)2GaCl: A Redox-Active Gallium Complex

et al. 2018

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Abstract:We report the synthesis of a gallium complex incorporating redox-active pyridyl nitroxide ligands. The (pyNO − ) 2 GaCl complex was prepared in 85% yield via a salt metathesis route and was characterized by 1 H and 13 C NMR spectroscopies, X-ray diffraction, and theory. UV-Vis absorption spectroscopy and electrochemistry were used to access the optical and electrochemical properties of the complex, respectively. Our discussion focuses primarily on a comparison of the gallium complex to the corresponding aluminum derivative and shows that although the complexes are very similar, small differences in the electronic structure of the complexes can be correlated to the identity of the metal.

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“…Gratifyingly, the action of TEMPO upon both these species evidenced SET characteristics with almost instantaneous extinction of the red colour associated with TEMPO. Monitoring by 1 H NMR spectroscopy revealed that compound 1 had undergone a well-precedented alkyl coupling to form n-octane, [7c] while compound 2, in reactivity reminiscent of that reported for group 13 hydrides, [9] provided a pronounced bubbling of molecular dihydrogen (eqn. 1).…”

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confidence: 99%