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

Abstract

The [(Cl3Ga)3N](3-) (1) anion, which is the sole example of a discrete chemical species containing a μ3-N atom bound only to gallium, was isolated from the reaction of Cl3Ga·N(SnMe3)3 with [GaCl4](1-). The analogous reaction of [GaCl4](1-) with (Me3Sn)3N afforded [(Cl3Ga)2NSnMe3](2-) (2), which is also an unprecedented anion containing a single μ3-N atom bound to only gallium and tin.

Room-Temperature Synthesis of GaN Driven by Kinetic Energy beyond the Limit of Thermodynamics

“…In contrast, the present nitridation method overcomes the reaction barrier through the production of a nonequilibrated molecular beam with high kinetic energy, in addition to the external thermal energy. Although many intermediate species are assumed, , a key intermediate in the nitridation reaction is considered to be the partly nitrided (GaCl 3 ) 3 N . A similar decrease in the activation energy was observed in previous study on the oxidation of a silicon surface …”

“…In contrast, the present nitridation method overcomes the reaction barrier through the production of a nonequilibrated molecular beam with high kinetic energy, in addition to the external thermal energy. Although many intermediate species are assumed, 13,28 a key intermediate in the nitridation reaction is considered to be the partly nitrided (GaCl 3 ) 3 N. 27 A similar decrease in the activation energy was observed in previous study on the oxidation of a silicon surface. 23 The product after treatment of the GaCl 3 layer on a quartz or silicon substrate surface at room temperature for 20 min exhibited a characteristic photoluminescence (PL) emission at 433 nm (2.86 eV) by excitation at 270 nm (Figure 3B).…”

“…Even a (GaCl 3 ) 3 (μ 3 -N) arrangement was recently reported. 27 Such small fragments containing Ga, N, and Cl atoms are still very reactive to such an extent that they quickly decompose into their hydroxide forms in the presence of a small amount of H 2 O in the air. The second reaction of eq 2-1 does involve many elementary steps, which include the formation of small fragments and their growth in the presence of reactive nitrogen radicals.…”

“…GaCl 3 is known as a strong Lewis acid that preferentially forms Ga–N coordination bonds. Even a (GaCl 3 ) 3 (μ 3 -N) arrangement was recently reported . Such small fragments containing Ga, N, and Cl atoms are still very reactive to such an extent that they quickly decompose into their hydroxide forms in the presence of a small amount of H 2 O in the air.…”