Issue 19, 2008

Structural diversity in bishydroxylamine complexes of gallium

Abstract

Reactions of bishydroxylamines of the type HON(R)CH2CH2N(R)OH (R = Me, tBu) with trimethyl- and triisopropylgallium gave bicyclic metalla cages of the formula R′2GaO(R)NCH2CH2N(R)OGaR′2 [R′ = Me, R = Me (3a), tBu (3b); R′ = iPr, R = Me (4a), tBu (4b)] with six-membered Ga2O2N2-rings. While the complexes show the same core constitution in the solid state, NMR spectra reveal the steric influence of the isopropyl substituent of the compounds 4a/4b on its behaviour in solution. The reaction of the sterically more demanding substituted tri-tert-butylgallium with HON(Me)CH2CH2N(Me)OH yielded a heterodimeric complex O′-[HON(Me)CH2CH2NH(Me)O(tBu2Ga)]-cyclo-(tBu2Ga)-O,N′-[ON(Me)CH2CH2N(Me)O] (5) with two gallium atoms of different surrounding and two different bishydroxylamine ligands, one doubly deprotonated and one protonated, but at one end in its tautomeric aminoxide form. Further condensation of 5 was observed to give a tricyclic compound cyclo-[(tBuGa)ON(Me)CH2CH2N(Me)O]2 (6) with a central Ga2O2N2 ring resulting from two Ga–N donor–acceptor bonds.

Graphical abstract: Structural diversity in bishydroxylamine complexes of gallium

Supplementary files

Article information

Article type
Paper
Submitted
26 Nov 2007
Accepted
22 Feb 2008
First published
25 Mar 2008

Dalton Trans., 2008, 2549-2556

Structural diversity in bishydroxylamine complexes of gallium

P. Bösing, A. Willner, T. Pape, A. Hepp and N. W. Mitzel, Dalton Trans., 2008, 2549 DOI: 10.1039/B718268F

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