Gold(I) and Gold(III) Complexes with the 1,1′-Bis(diethyldithiocarbamate)ferrocene Ligand

Abstract

The reaction of FcLi 2T MDA [Fc (h 5 -C 5 H 4 ) 2 Fe; TMDA tetramethylenediamine] with (S 2 CNEt 2 ) 2 affords the ferrocene derivative Fc(S 2 CNEt 2 ) 2 , which reacts with several gold(i) or gold(iii) precursors. Thus the treatment with [AuCl(tht)] (tht tetrahydrothiophene) or [Au(OTf)(PPh 3 )] (OTf trifluoromethanesulfonate) gives the complexes [Au 2 Cl 2 {Fc(S 2 CNEt 2{Fc(S 2 CNEt 2 ) 2 }] and [Au 2 {(C 6 F 5 ) 2 Cl} 2 -{Fc(S 2 CNEt 2 ) 2 }] were obtained by reaction of Fc(S 2 CNEt 2 ) 2 with [Au(C 6 F 5 ) 3 -(OEt 2 )] or [Au(C 6 F 5 ) 2 (m-Cl)] 2 , respectively. Fc(S 2 CNEt 2 ) 2 and [Au 2 Cl 2 {Fc-(S 2 CNEt 2 ) 2 }] have been characterised by X-ray diffraction studies. A new type of h 2 interaction found between the gold complex and the cyclopentadienyl ligand was studied by the extended Hückel method; it consists of carbon-to-gold electron donation in the absence of back-donation. The interaction was also detected by density functional calculations, which showed the energy of the three independent molecules to be comparable.

Perfluoroarylgold complexes

“…For the isolation of perfluorophenylgold derivatives ligands with different donor atoms, such as sulfur [Fc(S 2 CNEt 2 ) 2 , Fc(SPh) 2 Tables 1 and 2 [151][152][153][154][155][156][157][158][159][160][161][162][163].…”

Group 11 complexes with unsymmetrical P,S and P,Se disubstituted ferrocene ligands

“…This could indicate the presence of a weak g 2 interaction with the Cp ring, as we have observed in other gold or silver complexes with ferrocene moieties. 27, 28 In the lattice there are several Cl • • • H or Au • • • H interactions involving the protons of the phenyl and cyclopentadienyl groups. These contacts range from 2.7 to 2.9 A ˚and are mostly of acceptable linearity to be considered as hydrogen bonds.…”

The Chemistry of Gold

“…23 shows some of these complexes. Other complexes with these polydentate ligands include species with diphosphine ligands such as the complex with the 2-thioxo-1.24b), or the gold complex [Au 2 Cl 2 {Fc(S 2 CNEt) 2 ][171] with the bis(dithiocarbamate)ferrocene ligand in which there are h 2 interactions between the gold(I) atoms and the cyclopentadienyl ligands(Figure 1.24c).…”