Reduction of [Cp*Sb]4 with subvalent main group metal reductants - syntheses and structures of [(L1Mg)4(Sb4)] and [(L2Ga)2(Sb4)] containing edge-missing Sb4 units

[Cp*Sb]4 (Cp*=C5Me5) reacts with [L1Mg]2 and L2Ga with formation of [(L1Mg)4(μ4,η1:2:2:2‐Sb4)] (L1=iPr2NC[N(2,6‐iPr2C6H3)]2, 1) and [(L2Ga)2(μ,η2:2‐Sb4)] (L2=HC[C(Me)N(2,6‐iPr2C6H3)]2, 2). The cleavage of the Sb−Sb and Sb−C bonds in [Cp*Sb]4 are the crucial steps in both reactions. The formation of 1 occurred by elimination of the Cp* anion and formation of Cp*MgL1, while 2 was formed by reductive elimination of Cp*2 and oxidative addition of L2Ga to the Sb4 unit. 1 and 2 were characterized by heteronuclear NMR spectroscopy and single‐crystal X‐ray diffraction, and their bonding situation was studied by quantum chemical calculations.

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