Synthesis and Coordination Behavior of a Hybrid Phosphanylferrocene Amidine Ligand

Abstract

The combination of different donor moieties often results in unconventional coordination behavior. This contribution describes the synthesis of a new hybrid ligand, phosphanylferrocene amidine Ph2PfcN=CHNMe2 (1; fc = ferrocene‐1,1¢‐diyl), and its coordination behavior toward the light platinum metals. Reacting compound 1 with [PdCl2(MeCN)2] produced the chelate complex [PdCl2(1‐κ2P,N)] and the bis(phosphane) complex trans‐[PdCl2(1‐κP)2], depending on the ligand‐to‐metal stoichiometry. Halide removal from [PdCl2(1‐κ2P,N)] with Na[BARF] afforded the chloride‐bridged dimer [Pd2(μ‐Cl)2(1‐κ2P,N)2][BARF]2, which was presumably in equilibrium with the mononuclear κ3‐complex [PdCl(1‐κ3Fe,P,N)][BARF] in solution (BARF = tetrakis[3,5‐bis(trifluoromethyl)phenyl]borate). The reactions of 1 with the isoelectronic precursors [(arene)MCl(μ‐Cl)]2 (M/arene = Ru(II)/p‐cymene, and Rh(III)/C5Me5) generated the respective bridge‐cleavage products [(arene)MCl2(1‐κP)], which transformed into the P,N‐chelate complexes [(arene)MCl(1‐κ2P,N)][BARF] when treated with Na[BARF] as a chloride scavenger. All this suggests preferential coordination the phosphane moiety to soft metal ions, while the coordination of the amidine moiety can be induced through changing the reaction stoichiometry or by generating a vacant coordination site at the metal ion. The compounds were characterized using a combination of standard spectroscopic methods (multinuclear NMR, IR, and ESI MS) and single‐crystal X‐ray crystallography, and compounds 1 and 3 were further studied by cyclic voltammetry.