TY - JOUR
T1 - Reactions of Low-Valent Gallium Species with Organic Azides
T2 - Formation of Imido-, Azoimido-, and Tetrazene Complexes
AU - Zhang, Yihu
AU - Dodonov, Vladimir A.
AU - Chen, Weixing
AU - Zhang, Shuangshuang
AU - Roesky, Peter W.
AU - Zhao, Yanxia
AU - Fedushkin, Igor L.
AU - Yang, Xiao Juan
N1 - Publisher Copyright:
© 2023 American Chemical Society.
PY - 2023/4/24
Y1 - 2023/4/24
N2 - The reactivity of two α-diimine-ligated digallanes, [L2-Ga-GaL2-] (La = [(2,6-iPr2C6H3)NC(CH3)]2, dpp-dad, 1; Lb = 1,2-[(2,6-iPr2C6H3)NC]2C10H6, dpp-bian, 2), and a gallylene, [(La)2-GaNa(THF)3] (3), toward organic azides was studied. Reaction of digallane 1 or 2 with trimethylsilyl azide (Me3SiN3), 2-azido-benzonitrile (2-CNC6H4N3), or tosylazide (TosN3) results in imido-bridged complexes, [(La)·-Ga(μ-NSiMe3)2Ga(La)·-] (4) [(Lb)·-Ga(μ-NSiMe3)2Ga(Lb)·-] (5), [(Lb)·-Ga(μ-2-CNC6H4N)2Ga(Lb)·-] (6), and [(Lb)·-Ga(μ-NTos)2Ga(Lb)·-] (7), with elimination of dinitrogen. Treatment of 1 or 2 with 1-adamantyl azide (1-AdN3), on the other hand, affords the unsymmetrical dinuclear complexes [(La)·-Ga(NAd)(N3Ad)Ga(La)·-] (8) and [(Lb)·-Ga(NAd)(N3Ad)Ga(Lb)·-] (9), which contain both imido and triazene bridges. Different from the Ga(II) complexes 1 and 2, the reactions of Ga(I) species 3 with benzylazide or trimethylsilyl azide result in the tetrazene complex {Na(THF)}2[(La)2-Ga(benzyl-N4-benzyl)]2 (10) and amide complex {Na(THF)4}[(La)2-Ga(NHSiMe3)(benzyl)] (11). It is likely that these latter transformations proceed via the transient formation of the corresponding Ga═N imide complex, which undergoes either cycloaddition with a second azide (to form 10) or activation of the C-H bond of methyl in one solvent toluene molecule (to yield 11).
AB - The reactivity of two α-diimine-ligated digallanes, [L2-Ga-GaL2-] (La = [(2,6-iPr2C6H3)NC(CH3)]2, dpp-dad, 1; Lb = 1,2-[(2,6-iPr2C6H3)NC]2C10H6, dpp-bian, 2), and a gallylene, [(La)2-GaNa(THF)3] (3), toward organic azides was studied. Reaction of digallane 1 or 2 with trimethylsilyl azide (Me3SiN3), 2-azido-benzonitrile (2-CNC6H4N3), or tosylazide (TosN3) results in imido-bridged complexes, [(La)·-Ga(μ-NSiMe3)2Ga(La)·-] (4) [(Lb)·-Ga(μ-NSiMe3)2Ga(Lb)·-] (5), [(Lb)·-Ga(μ-2-CNC6H4N)2Ga(Lb)·-] (6), and [(Lb)·-Ga(μ-NTos)2Ga(Lb)·-] (7), with elimination of dinitrogen. Treatment of 1 or 2 with 1-adamantyl azide (1-AdN3), on the other hand, affords the unsymmetrical dinuclear complexes [(La)·-Ga(NAd)(N3Ad)Ga(La)·-] (8) and [(Lb)·-Ga(NAd)(N3Ad)Ga(Lb)·-] (9), which contain both imido and triazene bridges. Different from the Ga(II) complexes 1 and 2, the reactions of Ga(I) species 3 with benzylazide or trimethylsilyl azide result in the tetrazene complex {Na(THF)}2[(La)2-Ga(benzyl-N4-benzyl)]2 (10) and amide complex {Na(THF)4}[(La)2-Ga(NHSiMe3)(benzyl)] (11). It is likely that these latter transformations proceed via the transient formation of the corresponding Ga═N imide complex, which undergoes either cycloaddition with a second azide (to form 10) or activation of the C-H bond of methyl in one solvent toluene molecule (to yield 11).
UR - http://www.scopus.com/inward/record.url?scp=85152682865&partnerID=8YFLogxK
U2 - 10.1021/acs.inorgchem.2c04297
DO - 10.1021/acs.inorgchem.2c04297
M3 - Article
C2 - 37036292
AN - SCOPUS:85152682865
SN - 0020-1669
VL - 62
SP - 6288
EP - 6296
JO - Inorganic Chemistry
JF - Inorganic Chemistry
IS - 16
ER -