Reduction of Digallane [(dpp‐bian)GaGa(dpp‐bian)] with Group 1 and 2 Metals

The reduction of digallane [(dpp‐bian)GaGa(dpp‐bian)] ( 1 ) (dpp‐bian=1,2‐bis[(2,6‐diisopropylphenyl)imino]acenaphthene) with lithium and sodium in diethyl ether, or with potassium in THF affords compounds featuring the direct alkali metal–gallium bonds, [(dpp‐bian)GaLi(Et 2 O) 3 ] ( 2 ), [(dpp‐bian)GaNa(Et 2 O) 3 ] ( 3 ), and [(dpp‐bian)GaK(thf) 5 ] ( 7 ), respectively. Crystallization of 3 from DME produces compound [(dpp‐bian)GaNa(dme) 2 ] ( 4 ). Dissolution of 3 in THF and subsequent crystallization from diethyl ether gives [(dpp‐bian)GaNa(thf) 3 (Et 2 O)] ( 5 ). Ionic [(dpp‐bian)Ga] − [Na([18]crown‐6)(thf) 2 ] + ( 6 a ) and [(dpp‐bian)Ga] − [Na(Ph 3 PO) 3 (thf)] + ( 6 b ) were obtained from THF after treatment of 3 with [18]crown‐6 and Ph 3 PO, respectively. The reduction of 1 with Group 2 metals in THF affords [(dpp‐bian)Ga] 2 M(thf) n (M=Mg ( 8 ), n =3; M=Ca ( 9 ), Sr ( 10 ), n =4; M=Ba ( 11 ), n =5). The molecular structures of 4 – 7 and 11 have been determined by X‐ray crystallography. The GaNa bond lengths in 3 – 5 vary notably depending on the coordination environment of the sodium atom.