Synthesis and Thermolysis of Alkyl- and Phenylamido Diphenylgallium, [Ph₂GaN(H)R]₂. Isolation and Structural Characterization of (PhGaNMe)₇ and (PhGaNPh)₄

Abstract

Alkyl- and phenylamido diphenylgallium compounds, [Ph(2)GaN(H)R](2) (R = Me, 1; Et, 2; (n)Pr, 3; (i)Bu, 4; Ph, 5), were prepared from the reactions of Ph(3)Ga with the corresponding primary amines and aniline at elevated temperatures and were characterized by elemental analysis, mass spectroscopy, and (1)H NMR and IR spectroscopy. These dimeric compounds contained bridging amido groups and exhibited both trans and cis isomers in solution. Thermolysis of compounds 1 and 5 was carried out either without solvent or in dodecane solutions, and two clusters, (PhGaNMe)(7) 6 and (PhGaNPh)(4) 7, were isolated in 24% and 55% yields and characterized. The structure of 6 consisted of a heptameric Ga(7)N(7) core constructed with Ga(2)N(2) and Ga(3)N(3) rings, and the structure of 7 possessed a Ga(4)N(4) cubane core.

β‐Diketiminate Gallium Amides: Useful Synthons in Gallium Chemistry

“…Although there are previous reports of gallium diamides, they are mainly oligomeric compounds and the stabilization of monomeric molecules requires the use of bulky arylamides, and thus, their reactivity is limited. [12][13][14][15][16][17] To the best of our knowledge, only few structurally characterized gallium amides containing at least one terminal alkylamino group have been reported so far. Thus, two terminal tert-butylamino groups were observed in [{tBu(H)N} 2 Ga{µ-N(H) tBu}] 2 .…”

Synthesis and Structures of Gallium Amido Imido Phenyl Clusters (PhGa)4(NHiBu)4(NiBu)2 and (PhGa)7(NHMe)4(NMe)5

“…Pentane (10 mL) was added resulting in the formation of a colorless solution. After the solution was stored at −20 °C for 2 days, a colorless crystalline solid formed (0.12 g, 14% yield based on gallium) which was characterized as [Ph 2 GaN(H) i Bu] 2 by comparing its IR and 1 H NMR spectra with those of the authentic sample . The remaining compounds in the solution formed a glassy solid upon pentane evaporation, and the 1 H NMR spectrum showed a complex pattern.…”

“…We recently reported the structural characterization of two gallium−nitrogen clusters, (PhGaNPh) 4 and (PhGaNMe) 7 − and a hexamer [MeGaN(4-C 6 H 5 F)] 6 was facilitated by hydrocarbon elimination in the reactions of triorganylgallium with aniline or primary amines at elevated temperatures.…”

From “Parasitic” Association Reactions toward the Stoichiometry Controlled Gas Phase Synthesis of Nanoparticles: A Theoretically Driven Challenge for Experimentalists

“…The structural characteristics of the clusters are presented in Figure 5. Recently, Gladfelter120 proposed the existence of “needle‐like” structures of C 3v symmetry with n = 10, 13. In addition to the most stable structures from Ziegler's work, the needle‐like isomers were also considered.…”