PdMo3S4 cubane clusters [(CP*Mo)(3)(mu(3)-S)(4)Pd(L)][PF6] (Cp* = eta(5)-(CMe5)-Me-5; L = dba (2), ma (3); dba = dibenzylideneacetone, ma = maleic anhydride) showed high catalytic activity for the intramolecular hydroamination of aminoalkynes to afford the corresponding cyclic imines in good yields under mild conditions. A molecular structure of 3 has been determined by X-ray diffraction study.