Metal Complexes with Mono‐ and Bis{[bis(2‐pyridyl)amino]carbonyl}ferrocene Ligands

Abstract

The ligands {[bis(2‐pyridyl)amino]carbonyl}ferrocene (L1) and 1,1′‐bis{[bis(2‐pyridyl)amino]carbonyl}ferrocene (L2) have been prepared by treatment of the mono‐ or 1,1′‐bis(chlorocarbonyl)ferrocene derivatives with dipyridylamine in a 1:1 or 1:2 ratio, respectively. The ligand properties of these compounds towards group 11 and palladium complexes have been studied. Ligand L1 coordinates to these compounds to give four‐coordinate [Cu(L1)2]+, [PdCl2(L1)] and [Ag(OTf)(L1)(PR3)] or three‐coordinate [Ag(OTf)(L1)] and [Au(C6F5)(L1)] compounds. The ligand coordinates in a chelate fashion in all cases. The reactivity of L2 is somewhat different because coordination to copper or silver atoms can take place through several pyridine units either from different cyclopentadienido rings, as in [Cu(L2)]+, [Ag2(OTf)2(L2)] and [Ag(OTf)(L2)(PPh3)], or from the same cyclopentadienido ring, as in [Ag2(OTf)2(L2)(PPh3)2]. Coordination as a bridging ligand for four gold atoms has also been achieved in [Au4(C6F5)4(L2)] and [Au4(L2)(PPh3)4](OTf)4. The ligands and some complexes have been characterized by X‐ray diffraction studies and show the presence of several hydrogen bonds that lead to supramolecular structures.(© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2008)

Bridging ligands comprising two or more di-2-pyridylmethyl or amine arms: Alternatives to 2,2′-bipyridyl-containing bridging ligands

“…This was obtained by Ullmann coupling of 4,6-diiodopyrimidine and di-2-pyridylamine in around 30% (52) Organometallic bridging compounds were reported by Braga [117] and Concepción Gimeno [118] who studied bis{[di-2-pyridylamino]carbonyl}-cobaltocenium and ferrocene ligands, respectively. These were prepared by treating the diacid chloride of cobatacenium and ferrocene with di-2-pyridylamine to give 57a and 57b, respectively.…”

“…The coordination chemistry of 57b has been explored in great detail with Cu(I), Ag(I), and Au(I) precursors and displays a number of coordination modes that are dependent on the metal, stoichiometry, anions, and co-ligands. [118] which is positively charged and thus, anticipated to lead to highly cationic complexes. [117] Harmjanz and co-workers [119] have studied a series of cyclotriphosphazene-based ligand systems, one of which incorporates two di-2-pyridylamine chelating motifs, as models for coordination by structurally and electronically-related high molecular weight polyphosphazenes.…”

Synthesis and properties of new Mo(II) complexes with N-heterocyclic and ferrocenyl ligands

“…Crystals of both ferrocene derivatives of suitable quality for X-ray diffraction studies were grown from hexane diffusion into a CH 2 Cl 2 solution of the compound. The structure of L2 has been reported [16].…”

“…All experimental manipulations were carried out under nitrogen atmosphere using Schlenk techniques. The ligand {[bis(2-pyridyl)amino]carbonyl}ferrocene (L2) [16], was prepared, as reported, by the coupling reaction between FcCOCl [Fc ¼ (h 5 -C 5 H 5 )Fe(h 5 -C 5 H 4 )] [22] and 2,2 0 -dipyridylamine in a 1:1 ratio, in dichloromethane and in presence of NEt 3 . Complexes [MoBr(h 3 -C 3 H 5 )(CO) 2 (NCMe) 2 ] [12] and [MoBr(h 3 -C 3 H 5 )(CO) 2 (L1)] [13] were synthesized according to literature procedures.…”

“…Both 2,2 0 -dipyridylamine (L1) and 2-aminopyridine react with FcCOCl (Fc ¼ (h 5 -C 5 H 5 )Fe(h 5 -C 5 H 4 )), in a 1:1 ratio, in the presence of NEt 3 to give L2 ¼ {[bis(2-pyridyl)amino]carbonyl}ferrocene [16] and L3 ¼ N,N-bis(ferrocenecarbonyl)-2-aminopyridine, respectively. Crystals of both ferrocene derivatives of suitable quality for X-ray diffraction studies were grown from hexane diffusion into a CH 2 Cl 2 solution of the compound.…”