Monomeric Organogallium−Nitrogen Compounds. Chemistry of Et₂GaNH[C₆H₂(2,4,6-t-Bu)₃] with Decomposition to the Metallacycle {EtGaNH[C₆H₂(4,6-t-Bu)₂CMe₂CH₂-2]}₂ and of EtGa{NH[C₆H₂(2,4,6-t-Bu)₃]}₂

Abstract

Two monomeric gallium−nitrogen compounds, Et2GaNH[C6H2(2,4,6-t-Bu)3] and EtGa{NH[C6H2(2,4,6-t-Bu)3]}2, have been prepared by metathetical reactions between either Et2GaCl or EtGaCl2, as appropriate, and LiNH[C6H2(2,4,6-t-Bu)3] and have been characterized fully. Cryoscopic molecular weight studies demonstrated both compounds to be monomeric in benzene solution, whereas an X-ray structural study of the latter identified a monomer. The compound Et2GaNH[C6H2(2,4,6-t-Bu)3] decomposes at room temperature to form a new metallacyclic derivative GaEt3, and H2N[C6H2(2,4,6-t-Bu)3]. A 1H NMR spectral study and an X-ray structural study were used to elucidate its structure. The compound EtGa{NH[C6H2(2,4,6-t-Bu)3]}2 does not decompose to the metallacycle, but it reacts readily with GaEt3 to form Et2GaNH[C6H2(2,4,6-t-Bu)3].

Synthesis and Characterization of Monomeric Organogallium−Nitrogen Compounds, Et2GaNMe[C6H2(2,4,6-t-Bu)3], Me2GaNMe[C6H2(2,4,6-t-Bu)3], MeGa{NH[C6H2(2,4,6-t-Bu)3]}2, and Ga{NH[C6H2(2,4,6-t-Bu)3]}3

“…The new compound Et 2 GaNMe[C 6 H 2 (t - Bu) 3 ], which is closely related to the previously reported derivative Et 2 GaNH[C 6 H 2 (t - Bu) 3 ], was synthesized in 90% yield by a metathetical reaction between Et 2 GaCl , and LiNMe[C 6 H 2 (t-Bu) 3 ] in pentane and then fully characterized. Even though both gallium−nitrogen compounds are liquids at room temperature and are monomeric according to cryoscopic molecular weight studies in benzene solution in the concentration range of 0.04−0.08 m , they have very different chemical properties and 1 H NMR spectra.…”

“…The new derivative Et 2 GaNMe[C 6 H 2 (t - Bu) 3 ] was stable to decomposition at temperatures up to 120−130 °C. In contrast, Et 2 GaNH[C 6 H 2 (t - Bu) 3 ] decomposed at room temperature and formed the metallacyclic compound GaEt 3 , and H 2 N[C 6 H 2 (t-Bu) 3 ] . The 1 H NMR spectra of these two gallium−nitrogen monomers are also very different.…”

“…The derivative with three bulky substituents, Ga{NH[C 6 H 2 (t-Bu) 3 ]} 3 , was prepared by reacting GaCl 3 with excess LiNH[C 6 H 2 (t - Bu) 3 ] . This gallium−nitrogen product was soluble in pentane and benzene even though it decomposed at the unusually high temperature of 258−260 °C.…”

Catalytic Reduction of Carbon Dioxide Using Cationic Organoaluminum and -Gallium Compounds

“…Solvents were freshly distilled under N 2 from sodium, potassium, or sodium/potassium alloy and degassed twice prior to use or they were dispensed from a commercial solvent purification system. The compounds Et 2 GaCl, Ph 2 C 6 H 3 Li, Dipp*Li, and [Ph 3 C]­[CHB 11 Cl 11 ] were prepared according to literature procedures. All other reagents were obtained from commercial suppliers and used as received.…”

MCl2Molecules (M = Zn, Cd, Hg) Coordinated by Trifunctional E/P2-Based FLPs (E = Ga, In): Chelating Coordination of the Metal Atoms and Activation of M–Cl Bonds by E–Cl Interactions

“…IR spectra were recorded as KBr pellets on a Shimadzu Prestige 21 spectrometer and electron impact mass spectra on a Finnigan MAT 95 mass spectrometer. The Grignard reagent 2 , MeGaCl 2 , EtGaCl 2 , and MeInCl 2 were synthesized according to literature procedures. Commercially available ZnCl 2 was dried under vacuum (10 –3 mbar) at 120 °C for 5 h. AuCl­(SMe 2 ), CdCl 2 , and HgCl 2 were used as purchased.…”