[LAl(μ‐S₃)₂AlL]: A Homobimetallic Derivative of the Sulfur Crown S₈

Temperature‐Dependent Electron Shuffle in Molecular Group 13/15 Intermetallic Complexes

“…1 H NMR (C 6 D 6 , 300 MHz): d = 7.14 (m, 6 H, C 6 H 3 (iPr) 2 ), 4.78 (s, 1 H, g-CH-), 3 Synthesis of RGa(BiEt 2 ) 2 (4). Method 1: A solution of RGa (228 mg, 0.468 mmol) in toluene (10 mL) was added dropwise to a solution of Bi 2 Et 4 (250 mg, 0.468 mmol) in toluene (10 mL) and stirred for 1 h at ambient temperature.…”

“…[2] The powerful reducing activity of b-diketiminate aluminum and gallium complexes make them very unique, and they were used for the activation of small molecules such as azides, diimines, O 2 , S 8 , P 4 , acetylene, and others. [3] Reduction reactions of RGa with main-group metal compounds such as SnCl 2 [4] and Bi(OR'') 3 [5] yielded novel gallyl-supported tin clusters [Sn 7 {Ga(Cl)(R)} 2 ] and [Sn 17 {Ga(Cl)(R)} 4 ] and galla-dibismuthenes [{RGa(OR'')Bi} 2 ] (R'' = C 6 F 5 , SO 2 CF 3 ). These reactions proceeded straightforwardly with oxidation of the Group 13 metal and subsequent metal-metal bond formation.…”

“…Elemental analysis (C, H, N) of 3, however, confirms its analytically pure nature. The temperature sensitivity of M À E s-bonded compounds is well known; that is, [{Me 2 GaBi-(SiMe 3 ) 2 } 3 ] decomposes in non-coordinating solvents with formation of Me 3 Ga, Bi 2 (SiMe 3 ) 4 , and elemental Ga, whereas in coordination solvents the formation of (Me 3 Si) 3 Bi, Me 3 Ga, and an insoluble metallic precipitate was observed. [9d] We therefore investigated the thermal stability of 3 in C 6 D 6 by temperature-variable 1 H NMR spectroscopy.…”

Temperature‐Dependent Electron Shuffle in Molecular Group 13/15 Intermetallic Complexes

“…A triplet and a multiplet at 1.40 and 1.73 ppm confirm the presence of the ethyl groups. 4 , and elemental Ga, whereas in coordination solvents the formation of (Me 3 Si) 3 Bi, Me 3 Ga, and an insoluble metallic precipitate was observed.…”

“…[3] Reduction reactions of RGa with main-group metal compounds such as SnCl 2 [4] and Bi(OR'') 3 [5] yielded novel gallyl-supported tin clusters [Sn 7 {Ga(Cl)(R)} 2 ] and [Sn 17 {Ga(Cl)(R)} 4 ] and galla-dibismuthenes [{RGa(OR'')Bi} 2 ] (R'' = C 6 F 5 , SO 2 CF 3 ). These reactions proceeded straightforwardly with oxidation of the Group 13 metal and subsequent metal-metal bond formation.…”