The gallium(I) derivative [Ga({N(dipp)CMe}(2)CH)] (1; dipp = 2,6-diisopropylphenyl) undergoes facile oxidative addition reactions with various element-hydrogen bonds including N-H, P-H, O-H, Sn-H, and H-H bonds. This was demonstrated by its reaction with triphenyltin hydride, ethanol, water, diethylamine, diphenylphosphane, and dihydrogen. All products were characterized by means of single-crystal X-ray structure determination, NMR spectroscopy, IR spectroscopy, and mass spectrometry.

The synthesis of a new tetradentate bispidine ligand (LH2 = 2,2′-(1,5-dimethyl-3,7-diazabicyclo[3.3.1]nonan-3,7-diyl)diacetic acid), containing two tertiary amine and two carboxylic groups, is reported along with the preparation and characterization of the corresponding Cu(ii) and Fe(iii) complexes. The mononuclear [LCu(OH2)]·4H2O (1) complex contains a five-coordinate Cu(ii) centre, which adopt a square pyramidal geometry with the four donor atoms of the ligand (N2O2) occupying the equatorial plane and a water molecule occupying the axial position. An axial electron paramagnetic resonance (EPR) signature is observed for 1 (gx = 2.054, gy = 2.050, gz = 2.234; Ax = 18 × 10–4 cm–1, Ay = 20 × 10–4 cm–1, Az = 188 × 10–4 cm–1) in frozen methanolic solution (0.1 mM). Dimerization of 1 in concentrated solution (10 mM) was observed by EPR spectroscopy (g∥ = 2.24, g⊥ = 2.07, A∥ = 195 × 10–4 cm–1, and A⊥ = 12 × 10–4 cm–1 for each Cu centre). The structure of the dimeric species [LCu(OH2)]2 (1b) was determined by a combination of molecular mechanics with the simulation of the EPR spectrum (MM-EPR). The dimer has each Cu(ii) centre coordinated by the two amines and one carboxylate of one ligand (L), while the other carboxylate bridges to the second Cu(ii) centre; each coordination sphere is completed by an axial water ligand, with the Cu···Cu distance 5.5 Å (relative orientation from EPR simulation: α = 60°, β = 0°, γ = 25°). The aqueous reaction between the tetradentate ligand (L) and Fe(ii) leads to the formation of an oxo-bridged diiron(iii) complex, [LFe-(μ-O)-FeL] (2), with a Fe–O–Fe angle of 180° (dFe···Fe = 3.516 Å), as revealed by X-ray crystallography. The Mössbauer spectrum of 2 consists of one quadrupole doublet with an isomer shift (δ) of 0.37 mm s–1 and a quadrupole splitting (ΔEQ) of 0.73 mm s–1, which is consistent with S = 5/2 Fe(iii) centres. Variable-temperature magnetic susceptibility measurements show the presence of intramolecular antiferromagnetic interactions between the two Fe(iii) centres, with an exchange coupling constant J of –91(3) cm–1 (H = –2JS1·S2).

Keywords: Bismuth / Silicon / Lithium / Crystal structure analysis / Density functional calculations On reaction of BiBr 3 with Li(thf) 3 SiPh 2 tBu (1) in the corresponding ratios redox/metathesis reactions were observed, yielding dibismuthane (tBuPh 2 Si) 4 Bi 2 (2) and disilylbismuth halide (tBuPh 2 Si) 2 BiBr (3). The latter is a reaction intermediate in the formation of the dark-red 2. The X-ray crystal structures of 1-3 were determined by low-temperature X-ray diffraction. The Si 2 Bi-BiSi 2 core of 2 is in the semi-eclipsed conformation. No oligomerization of "nonthermochromic" 2 was observed. Compound 3 is a mixed substituted monomer with a pyramidal environment around the bismuth center. On the basis of quantum chemical calculations, the formation of tertiary bismuthane (tBuPh 2 Si) 3 Bi is not expected for steric reasons. According to DFT-optimized geometries of the simplified model systems n[(H 3 Si) 2 Bi] 2 (n = 1-3), the closed-shell attraction between intermolecular Bi centers in the chain provides a moderate elongation of the intramolecular Bi-Bi

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The neutral trigallane R(3)Ga(3)I(2) was obtained in high yields by reaction of "GaI" with the moderately sterically demanding lithium N,N'-dicyclohexylneopentylamidinate. Its chemical reactions with N-lithio-2-propanimine, sodium superhydride and elemental iodine were investigated. RI-DFT calculations have been performed to confirm the bonding situation. All compounds are characterised by crystal structure analysis and NMR-spectroscopy.