Suppressed aggregation: The unprecedented alumoxane hydrogensulfide [{LAl(SH)}2(μ‐O)] and the unique sulfide‐bridged compound [{LAl(SH)}2(μ‐S)] can be prepared from the easily accessible aluminum dihydride [LAlH2] (L=HC[(CMe)N(2,4,6‐Me3C6H2)]2−). Owing to the cis conformation of the terminal SH groups, these compounds represent ideal precursors for the synthesis of heterometallic compounds.

The 4,5-bis(diphenylphosphoranyl)-1,2,3-triazole [4,5-(P(E)Ph2)2tz] derivatives of indium {kappa3-N,N',E-[4,5-(P(E)Ph2)2(mu-tz)]InMe2}2 (E = O2, S3, Se4) were prepared in good yield. In addition, compound 5 (E = O, E' = Se) was obtained from 4 through the replacement of a selenium atom in the P-Se(In) moiety by an oxygen atom, giving the mixed-chalcogen complex. The crystal structures of 2 and 5 exhibit a central C4In2N6O2P4core with an almost planar arrangement (mean deviation = 0.019 and 0.042 A for 2 and 0.100 A for 5), while the C4In2N6S2P4 core in 3 is nonplanar (mean deviation = 0.223 A).

The cyclic alumosiloxane [{LAl(μ-O)(Ph(2)Si)(μ-O)}(2)] (3) and alumosilicate [{LAl(μ-O){((t)BuO)(2)Si}(μ-O)}(2)] (4) were obtained by reaction of the appropriate R(2)Si(OH)(2) precursor (R = Ph, O(t)Bu) with [{LAl(H)}(2)(μ-O)] (1), providing a nice illustration of the Loewenstein rule at work at the molecular level.

The syntheses and molecular structures of [M{N(SeP(i)Pr2)2-Se,Se'}2][M = Sn(2), Se(3)] are described, these complexes consist of discrete, monomeric molecules featuring MSe4 cores that comprise true square-planar geometries.

The preparation of novel alkali metal chalcogenides supported by multidentate nitrogen rich ligands is reported. Treatment of the ligand precursors [H{(4,5-(P(E)Ph(2))(2)tz}] (E = S (1a), Se (1b)) with organolithium reagents or elemental sodium and potassium in tetrahydrofuran (THF) leads to the isolation of 2-7 in high yields. These compounds were characterized by elemental analysis, IR spectroscopy, mass spectrometry, solution and solid-state multinuclear NMR spectroscopy, and single crystal X-ray diffraction analysis. In the solid state, 2, 4, and 5 are dimers that contain bimetallic six-membered (M(2)N(4)) rings (M = Li, Na). In 3, the discrete monomer [Li{4,5-(P(Se)Ph(2))(2)tz}(thf)(2)] (tz = 1,2,3-triazole) contains a five-membered CPSeLiN ring which adopts an envelope conformation. The polymeric arrangement [K{4,5-(P(S)Ph(2))(2)}tz](infinity) in 6 displays different bonding modes based on the hapticity of the ligand upon binding to the potassium atom. In compounds 2-6, the presence of secondary bonding features the alkali metal chalcogen bonds.