Reaction of the bulky arylgallium dichloride Ar’GaCl2 OV = 2,4,6-t-Bu3C6H2) with 2.2 equiv of Na[Co(CO)4] in Et2O solution affords the intermetallic derivative [Ga(Ar’){Co(CO4)2] (1). Interestingly, the corresponding reaction of Ar’GaCl2 With Na[Mn(CO)5] in Et2O solution affords a mixed crystal of the first digalloxane, [Ga(Ar’){Mn-(CO)5}]2O (2) and [Ga(Ar)(Cl){Mn(CO)5}] (3). The structures of 1-3 have been established by X-ray crystallography.