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L 1 Ga {L 1 = HC[C(Me)N(2,6- iPr 2 C 6 H 3 )] 2 } reversibly reacts with E 2 Ph 4 (E = Sb, Bi) in a temperature-dependent equilibrium reaction with insertion into the E-E bond and formation of L 1 Ga(EPh 2 ) 2 (E = Sb 1, Bi 2). Analogous findings were observed in the reactions of L 2 Ga {L 2 = (C 6 H 11 ) 2 NC[N(2,6- iPr 2 C 6 H 3 )] 2 } with E 2 R 4 (R = Ph, Et), yielding L 2 Ga(EPh 2 ) 2 (E = Sb 3, Bi 4) and L 2 Ga(EE 2 ) 2 (E = Sb 5, Bi 6). 1-3 and 5 were isolated by fractional crystallization at low temperature, whereas 4 and 6 could not be isolated in their pure form even at low temperature. In contrast, reactions of [Cp*Al] 4 (Cp* = C 5 Me 5 ) with Sb 2 R 4 (R = Ph, Et) and Bi 2 E 4 did not proceed with insertion into the E-E bonds but with formation of (Cp*Al) 3 E 2 (E = Sb, 7; Bi, 8), whereas the reaction with Bi 2 Ph 4 yielded metallic bismuth. 8 was also formed in the reaction of [Cp*Al] 4 and BiE 3 at ambient temperature, whereas the analogous reaction of [Cp*Al] 4 with SbE 3 did not yield 7 even under drastic reaction conditions (120 °C, 3 days). In contrast, Cp*Ga and Sb 2 R 4 (R = Ph, Et) were found to react only at elevated temperature (120 °C) with formation of antimony metal.

Comprehensive Study on Reactions of Group 13 Diyls with Tetraorganodipentelanes