β‐Diketiminate Gallium Amides: Useful Synthons in Gallium Chemistry

Abstract

The facile preparation of β-diketiminate gallium amides with general formulas of either LGa(NHR) 2 {L = [HC{C(Me)N-(Ar)} 2 ]-, Ar = 2,6-iPr 2 C 6 H 3 ; R = Et (1), iPr (2), nBu (3), Ph (4)} or LGa(NHR)Cl [R = tBu (5); Et (6)] was accomplished by the reaction of LGaCl 2 with the lithium salt of the corresponding amine in 1:2 (1-4) or 1:1 (5, 6) molar ratios. Compounds 1-6 are useful synthons for further synthesis, as the amide substituents are excellent leaving groups, and the resulting amines can be cleanly and easily removed from the reaction matrix. To demonstrate this, compounds 1 and 5 were treated with ethanol, leading to the alcoholysis products LGa(OEt) 2

Monomeric Germanium(II) Amides Bearing β‐Diketiminato Ligands: Synthesis, Structural Characterization, and Thermal Properties

“…By comparison, the N–H bond chemical shift in 4 is smaller than that of 3 , which is likely due to bulky isopropyl groups on the aromatic rings. These chemical shifts are in good agreement with previously reported N–H signals for LGeNH(2,6‐ i Pr 2 C 6 H 3 ) ( δ = 5.64 ppm),9 L*GeNH(2,6‐ i Pr 2 C 6 H 3 ) ( δ = 4.85 ppm),10 and the gallium(III) amide LGa(NHPh) 2 ( δ = 6.16 ppm) 23d…”

“…Compounds 1 – 3 have melting points above 200 °C, and 4 melts at about 168 °C. In the FTIR spectra of 1 – 4 , N–H stretching bands appear at 3377, 3321, 3365, and 3348 cm –1 , respectively, and are comparable to the N–H group of LGeNH 2 (3333 cm –1 )6 and LGa(NH 2 ) 2 (3359 cm –1 ),24 and the N–H vibrations observed for LGa(NHEt) 2 , LGa(NH i Pr) 2 , LGa(NH n Bu) 2 , LGa(NHPh) 2 , and LAl(NHEt) 2 (3371–3381 cm –1 ) 23d. For 1 – 4 , the 1 H NMR spectra exhibit broad signals ( δ = 5.00 ppm for 1 , 5.08 ppm for 2 , 6.13 ppm for 3 , and 6.06 ppm for 4 ), which can be assigned to the N–H proton.…”

Synthetic and Structural Studies of Donor-Functionalized Alkoxy Derivatives of Gallium

“…Synthesis of [Cl(Me)Ga(O t Bu)] 2 (7). tert-Butanol (0.55 cm 3 , 5.8 mmol) was added to a solution of 2 (0.19 g, 0.3 mmol) in toluene (20 cm 3 ) which was prepared in situ.…”

Unprecedented gallium–nitrogen anions: synthesis and characterization of [(Cl3Ga)3N]3− and [(Cl3Ga)2NSnMe3]2−

“…Hydrolysis of GaCl 3 and the Ga-N bond with H 2 O in amides like the (b-diketiminate)Ga(NHR) 2 complexes are well known. 11 Comparison of the diffuse reflectance spectrum of the crystals of (Me 4 N) 3 1 with that of the initial precipitate (Fig. S-2 †) suggests that (Me 4 N) 3 1 is present in the precipitate prior to crystallization along with other species.…”