Azobenzene Reduction and Derivatization and Al–H Bond Insertion with β‑Diketiminate Gallium(I) Complexes
Huanhuan Dong, Connor Bourne, Aidan P. McKay, Alexandra M. Z. Slawin, David B. Cordes, Andreas Stasch
TL;DR
This paper explores new gallium(I) complexes and their reactions with azobenzene and aluminum hydrides, revealing structural transformations and coordination patterns.
Contribution
The study introduces new β-diketiminate gallium(I) complexes and their reactivity with azobenzene and aluminum hydrides, leading to novel gallium(III) and Ga–Al-bonded complexes.
Findings
Gallium(I) complexes [(EtDipnacnac)Ga] 2a and [iPrDipnacnac)Ga] 2b were synthesized with varying yields based on ligand substitution.
Azobenzene reacted with gallium(I) complexes to form gallium(III) complexes with N,ortho-C(H)-chelating coordination.
Complex 2a reacted with aluminum hydrides to form Ga–Al-bonded complexes and a gallium hydride derivative.
Abstract
Using backbone modification of popular β-diketiminate ligands, RDipnacnac = HC(RCNDip)2, with R = Et, iPr (Dip = 2,6-iPr2C6H3), we have prepared the new β-diketiminate gallium(I) complexes [(EtDipnacnac)Ga] 2a and [( iPrDipnacnac)Ga] 2b by salt metathesis/reduction using “GaI” in moderate to good (68%, 2a) and poor (10%, 2b) isolated yields, respectively, highlighting the influence of the ligand backbone substitution on the reaction success. The gallium(I) complexes were converted with azobenzene to the gallium(III) complexes [(RDipnacnac)Ga{(C6H5)NNPh}] 4a (R = Et) and 4b (R = iPr) with reduced former azobenzene fragments showing an N,ortho-C(H)-chelating coordination to the Ga centers. Complex 4a was further converted to its C–H-activated tautomer [(EtDipnacnac)Ga{(C6H4)N(H)NPh}] 5, and reaction with DMSO and benzaldehyde afforded…
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Taxonomy
TopicsSynthesis and characterization of novel inorganic/organometallic compounds · Organometallic Complex Synthesis and Catalysis · Catalytic C–H Functionalization Methods