Combining a phosphinoferrocene fragment with flexible multidonor moieties affords novel, flexible multidonor pro-ligands. This contribution describes the synthesis of two structurally similar functional phosphines, Ph2PfcNHC(O)CH2PPh2 (1) and Ph2PfcNHCH2CH2PPh2 (2, fc...

Ru(ii) and Rh(iii) complexes of the primary phosphinecarboxamide FcNHC(O)PH2 undergo facile dehydrohalogenation to produce phosphide-bridged dimers as syn and anti isomers.

Introducing a ferrocene moiety into a molecule results in the incorporation of a metal center and a redox active moiety. This contribution describes the synthesis of FcN(CH 2 PPh 2 ) 2 (1; Fc = ferrocenyl), a ferrocene analog of the widely studied bisphosphane pincer ligands, RN(CH 2 PPh 2 ) 2 . Compound 1 was studied as a ligand in complexes of Group 10 and 11 metal ions. The following compounds were synthesized and characterized using a combination of spectroscopic methods and single-crystal X-ray diffraction analysis: the square planar complexes [MX 2 (1-k 2 P,P')] (M/X = Ni/Cl, Pd/Cl, Pd/Br, Pd/I and Pt/ Cl) and the tetrahedral complexes [M(1-k 2 P,P') 2 ]X (M/X = Cu/PF 6 , Ag/SbF 6 and Au/SbF 6 ). Furthermore, a pair of open and cyclic digold(I) complexes containing bis-phosphane 1 as a P,Pbridging ligand, viz. [(μ(P,P')-1)(AuCl) 2 ] and [(μ(P,P')-1) 2 Au 2 ][SbF 6 ] 2 , were isolated. Ligand 1, the corresponding phosphane selenide 1-Se and all complexes (except for the poorly soluble [(μ(P,P')-1) 2 Au 2 ][SbF 6 ] and unstable [Ag(1k 2 P,P') 2 ][SbF 6 ]) were further analyzed by cyclic voltammetry.

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.

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