Synthesis, Structure, and Reactivity of Ga-Substituted Distibenes and Sb-Analogues of Bicyclo[1.1.0]butane

5 years ago

Synthesis, Structure, and Reactivity of Ga-Substituted Distibenes and Sb-Analogues of Bicyclo[1.1.0]butane

Walter Frank, Anton S. Nizovtsev, Stephan Schulz, Chelladurai Ganesamoorthy, Lars Tuscher, Christoph Wölper, Julia Krüger, Christoph Helling

Monovalent gallanediyl LGa {L=HC[C(Me)N(2,6-iPr2C6H3)]2} reacts with SbX3 to form the Ga-substituted distibenes [(LGaX)2Sb2] (X=NMeEt 1, Cl 2). Upon heating, 2 reacts to the bicyclo[1.1.0]butane analogue [(LGaCl)2(μ,η1:1-Sb4)] 3 containing a [Sb4]2− dianion. Moreover, 2 reacts with Li amides LiNR2 in salt elimination reactions that form the corresponding amido-substituted compounds 1 and [(LGaNMe2)2Sb2] 4, whereas reactions of 4 and [(LGaNMe2)2(μ,η1:1-Sb4)] 5 with two equivalents of GaCl3 resulted in the formation of 2 and 3, respectively. 1, 2 and 3 were characterized by 1H and 13C NMR spectroscopy, elemental analysis, and single crystal X-ray diffraction. In addition, their bonding situation was analyzed by quantum chemical calculations. Gallium-antimony compounds: LGa reacts with SbX3 to form Ga-substituted distibenes [(LGaX)2Sb2] (NMeEt 1, Cl 2, NMe2 4). Compounds 2 and 4 were thermally converted into the corresponding tetrastibines [(LGaX)2(μ,η1:1-Sb4)] (Cl 3, NMe2 5). Salt elimination reactions of 2 with Li amides yielded amido-substituted compounds 1 and 4, whereas amide/chloride exchange reactions of 4 and 5 with GaCl3 yielded 2 and 3. Quantum chemical calculations revealed the bonding situation within the complexes.

Publisher URL: http://onlinelibrary.wiley.com/resolve/doi

DOI: 10.1002/chem.201701248