Synthesis and Structural Characterisation of an N‐Phosphanyl Ferrocene Carboxamide and its Ruthenium, Rhodium and Palladium Complexes

Abstract

Abstract[((Diphenylphosphanyl)amino)carbonyl]ferrocene (1) has been synthesized and coordinated to light platinum metals, ruthenium, rhodium and palladium, in diverse coordination modes. Specifically, compound 1 was used to prepare the following phosphane complexes, [(η6‐mes)RuCl2(1‐κP)], [(η5‐C5Me5)RhCl2(1‐κP)], trans‐[PdCl2(1‐κP)2], and [(LNC)PdCl(1‐κP)] (mes=mesitylene, LNC=[2‐(dimethylamino‐κN)methyl]phenyl‐κC1). They were subsequently converted into cationic O,P‐chelate complexes by halide abstraction with AgClO4 and into neutral O,P‐chelate complexes by deprotonation with potassium tert‐butoxide. All coordination compounds and phosphane chalcogenides 1E (P‐bound chalcogen atom E=O, S and Se), which were also synthesised, were structurally characterised using spectroscopic methods (IR, multinuclear NMR and ESI MS) and single‐crystal X‐ray diffraction analysis. The electrochemical behaviour of the prepared compounds was studied by cyclic voltammetry, and the (LNC)Pd‐1 complexes were further studied by Mössbauer spectroscopy.

Low-Dimensional Architectures in Isomeric cis-PtCl2{Ph2PCH2N(Ar)CH2PPh2} Complexes Using Regioselective-N(Aryl)-Group Manipulation

“…In continuation of these studies, we report here our work on the regioselective positioning of amide/hydroxy and methyl groups within a series of aminomethylphosphines, both as the free ligands and when coordinated to a square-planar Pt(II) metal centre. Our rationale for introducing an -C(O)NH-group is based on the known use of this functionality in supramolecular chemistry [23] and, furthermore, the recent interest in amide-modified phosphines for their variable coordination chemistry [24][25][26], binding nitroaromatics [27], and relevance to catalysis based on Pd [28]. Our choice of metal fragment in this work, "cis-PtCl2", is based on its capability to support a relatively small bite angle diphosphine ligand in a cis, six-membered ring conformation, and to provide up to two "acceptor" sites for potential H-bonding [29].…”