In summary, we report reacOons of a Zn-Zn bonded complex, Cp*ZnZnCp*, with a series of main group carbene analogues bearing on low-valent Al, Ga, and Si centers. In each case, the reacOons occur with addiOon of the Zn-Zn bond to the low-valent centre, increasing the coordinaOon number from 2 to 4.