Synthesis and characterization of transition metal complexes of thiophene-2-methylamine: X-ray crystal structure of palladium (II) and platinum (II) complexes and use of palladium(ll) complexes as pre-catalyst in Heck and Suzuki cross-coupling reactions

摘要

The reactions of thiophene-2-(N-diphenylphosphino)methyiamine, Ph2PNHCH2-C4H3S, 1 and thiophene-2-[N,N-bis(diphenylphosphino)methylamine], (Ph2P)2NCH2-C4H3S, 2, with MCI2(cod) (M = Pd, Pt; cod = 1,5-cyclooctadiene) or [Cu(CH3CN)4]PF6 yields the new complexes [M(Ph2PNHCH2-C4H3S)2CI2], M = Pd 1 a, Pt 1 b, [Cu(Ph2PNHCH2-C4H3S)4]PF6,1c, and [M(Ph2P)2NCH2-C4H3S)CI2], M = Pd 2a, Pt 2b, {Cu[(Ph2P)2NCH2-C4H3S]2}PF6,2c, respectively. The new compounds were isolated as analytically pure crystalline solids and characterized by ~(31)P-, ~(13)C-, ~1H-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.