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The rare-earth metal hydroxylamide compound Y[N(SiHMe2)2]2[ONBn2][THF] (1) was prepared by the silylamide elimination pathway from the reaction of N,N-dibenzylhydroxylamine, Bn2NOH (Bn = CH2C6H5), with Y[N(SiHMe2)2]3[THF]2and was characterised by multinuclear NMR spectroscopy and elemental analysis. The compounds [Cp2Y(ONBn2)]2(2a) [Cp2Sm(ONBn2)]2(2b) were obtained by the reactions of MCp3(M = Y, Sm) with Bn2NOH. The trinuclear compound Cp5Y3[ON(Me)CH2CH2(Me)NO]2(3) was obtained by the reaction of YCp3and the bishydroxylamine HON(Me)CH2CH2(Me)NOH. 2a, 2band 3were characterised by NMR spectroscopy, single-crystal X-ray diffraction and elemental analysis. In all these complexes side-on-coordination of the hydroxylamide units was observed. The compounds are of dynamic nature in solution. [ABSTRACT FROM AUTHOR]

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. [ABSTRACT FROM AUTHOR]

A general route for the functionalization of P4mediated by four-membered phosphorus–nitrogen–metal heterocycles is introduced yielding novel phosphorus-rich clusters. [ABSTRACT FROM AUTHOR]

The first homoleptic anions of hydroxylaminato ate-complexes of yttrium and samarium of the formulae K[M(ONiPr2)4] (M = Y, Sm) have been prepared and structurally characterised featuring variations of the hapticity of their ONiPr2 ligands leading to different chain connectivities in their solid state aggregates. [ABSTRACT FROM AUTHOR]