Synthesis and structural characterization of a series of dimeric metal(II) imido complexes {M(mu-NAr(#))}2 [M = Ge, Sn, Pb; Ar(#) = C6H3-2,6-(C6H2-2,4,6-Me3)2] and the related monomeric primary amido derivatives M{N(H)Ar(#)}2 (M = Ge, Sn, Pb): spectroscopic manifestations of secondary metal-ligand interactions.

The solvent-free reaction of M{N(SiMe(3))(2)}(2) (M = Ge, Sn, or Pb) with the sterically encumbered primary amine 2,6-dimesitylaniline Ar(#)NH(2) [Ar(#) = C(6)H(3)-2,6(C(6)H(2)-2,4,6-Me(3))(2)] at ca. 165-175 degrees C afforded the highly colored imido dimers {M(mu-NAr(#))}(2), where M = Ge (1), Sn (2), or Pb (3), with disilylamine elimination. The compounds were characterized by single-crystal X-ray crystallography and heteronuclear NMR spectroscopy.

The selective preparation of an aluminum oxide and its isomeric C-H-activated hydroxide.

An aluminum oxide [LAlO]2 (1) has been prepared by the oxidative addition of aluminum(I) monomer LAl (L = HC[(CMe)(NAr)]2, Ar = 2,6-iPr2C6H3) with molecular oxygen. The short Al-O bonds in Al2(mu-O)2 result in short Al..

Two types of intramolecular addition of an Al-N multiple-bonded monomer LAlNAr' arising from the reaction of LAl with N3Ar' (L = HC[(CMe)(NAr)]2, Ar' = 2,6-Ar2C6H3, Ar = 2,6-iPr2C6H3).

The reaction of beta-diketiminated aluminum(I) monomer LAl with a large bulky azide N3Ar' (L = HC(CMeNAr)2, Ar' = 2,6-Ar2C6H3, Ar = 2,6-iPr2C6H3) in the temperature range from -78 degrees C to room temperature affords two different isomers 2 and 3, which have been characterized by spectroscopic and X-ray structural analyses, as well as elemental analysis. The variable-temperature 1H NMR kinetic studies of this reaction indicate the existence of the monomer LAlNAr' (1) at low temperature and the thermal stability of the compounds increases in the order of 1 < 2 < 3.