A General Route to Metal-Substituted Dipnictenes of the Type [L(X)M]2 E2.

Two equivalents of LGa (L=HC[C(Me)N(2,6-iPr2 C6 H3 )]2 ) reacted with PX3 (X=Cl, Br) with insertion into two P-X bonds and formation of [L(X)Ga]2 PX (X=Cl 1, Br 2), whereas the analogous reaction with AsCl3 occurred with twofold insertion and subsequent elimination of LGaCl2 and formation of the Ga-substituted diarsene [L(Cl)Ga]2 As2 (3). Analogous findings were observed in the reactions with Me2 NAsCl2 , yielding the unsymmetrically-substituted diarsene [L(Cl)Ga]As=As[Ga(NMe2 )L] (4). The reaction of As(NMe2 )3 with LGa gave [L(Me2 N)Ga]2 As2 (5) after heating at 165 °C for five days, whereas the reaction with LAl gave [L(Me2 N)Al]2 As2 (6) after heating at only 80 °C for one day. Finally, two equivalents of LGa reacted with Bi(NEt2 )3 to give [L(Et2 N)Ga]2 Bi2 (7). Complexes 1-7 were characterized by NMR spectroscopy (1 H, 13 C, 31 P), elemental analysis, and single-crystal X-ray diffraction (except for 1 and 5). The bonding situations in 4, 6, and 7 were analyzed by quantum chemical calculations.

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

Monovalent gallanediyl LGa {L=HC[C(Me)N(2,6-iPr2 C6 H3 )]2 } reacts with SbX3 to form the Ga-substituted distibenes [(LGaX)2 Sb2 ] (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 )2 Sb2 ] 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 1 H and 13 C NMR spectroscopy, elemental analysis, and single crystal X-ray diffraction. In addition, their bonding situation was analyzed by quantum chemical calculations.

A Gallium-Substituted Distibene and an Antimony-Analogue Bicyclo[1.1.0]butane: Synthesis and Solid-State Structures.

RGa {R=HC[C(Me)N(2,6-iPr2C6H3)]2} reacts with Sb(NMe2)3 with insertion into the Sb-N bond and elimination of RGa(NMe2)2 (2), yielding the Ga-substituted distibene R(Me2N)GaSb=SbGa(NMe2 )R (1). Thermolysis of 1 proceeded with elimination of RGa and 2 and subsequent formation of the bicyclo[1.1.0]butane analogue [R(Me2N)Ga]2Sb4 (3).