The reactions of thiophene-2-(N-diphenylphosphino)methylamine, Ph2PNHCH2-C4H3S, 1 and thiophene-2-[N,N-bis(diphenylphosphino)methylamine], (Ph2P)(2)NCH2-C4H3S, 2, with MCl2(cod) (M = Pd, Pt; cod = 1,5-cyclooctadiene) or [Cu(CH3CN)(4)]PF6 yields the new complexes [M(Ph2PNHCH2-C4H3S)(2)Cl-2], M = Pd 1a, Pt 1 b, [Cu(Ph2PNHCH2-C4H3S)(4)]PF6, 1c, and [M(Ph2P)(2)NCH2-C4H3S)Cl-2], M = Pd 2a, Pt 2b, (Cu[(Ph2P)(2)NCH2-C4H3S](2))PF6, 2c, respectively. The new compounds were isolated as analytically pure crystalline solids and characterized by (31)p-, C-13-, H-1-NMR and IR spectroscopy and elemental analysis. Furthermore, the solid-state molecular structures of representative palladium and platinum complexes of bis(phosphine)amine, 2a and 2b, respectively, were determined using single crystal X-ray diffraction analysis. The palladium complexes were tested as potential catalysts in the Heck and Suzuki cross-coupling reactions. Copyright (C) 2009 John Wiley & Sons, Ltd.