Bis-2-thienyldiethylaminophosphane as a Ligand in Late Transition Metal Complexes and its Transformation to Bis-2-thienylphosphane

Bis-2-thienyldiethylaminophosphane (C₄H₃S)₂PNEt₂ (1) is introduced as a ligand for late transition metal complexes ([(H₃C₄S)₂PNEt₂]_nMX_mL_p), with M = Ni(II), Au(I), Cu(I), Pd(II), Ir(I), X = Cl, Br and L = NCMe, COD, (2–7). Reactions of 1 with the late transition metal salts NiCl₂ ·dme, (Me₂S)AuCl, CuCl, PdCl₂(PhCN)₂, and [Ir(COD)Cl]₂ yield the complexes [{(H₃C₄S)₂PNEt₂}₂ ·NiCl₂] (2), [(H₃C₄S)₂PNEt₂ ·AuCl] (3) [(H₃C₄S)₂PNEt₂ ·CuCl(CH₃CN)]₂ (4), [{(H₃C₄S)₂PNEt₂}₂ ·PdCl₂] (5), [{(H₃C₄S)₂PNEt₂}₂ ·PdCl₂]₂ (6), and [(H₃C₄S)₂PNEt₂ ·IrCl(COD)] (7). In addition, the transformation of 1 to the valuable chlorine-substituted starting material (H₃C₄S)₂PCl (8) and the related conversion of 8 to the secondary phosphane (H₃C₄S)₂PH (9) is reported. The complexes 2–7 are stable under inert gas conditions and were characterized by single-crystal X-ray studies, NMR spectroscopy, and elemental analysis.