Te–Te and Te–C bond cleavage occurs in reactions of monovalent LGa (L = [(2,6-i-Pr2-C6H3)NC(Me)]2CH) with Te, Ph2Te2and i-Pr2Te. (LGa-μ-Te)21, LGa(TePh)22and LGa(i-Pr)Tei-Pr3were characterized by heteronuclear NMR (1H,13C,125Te) and IR spectroscopy and by single crystal X-ray analyses.