Cristina Sarroca

Synthesis of silver(I) complexes with 1,1′-bis(diphenyl-phosphino)ferrocene (dppf). Crystal structures of [Ag(dppf)(PPh3)]ClO4·2CH2Cl2, [Ag(dppf)2]ClO4·2CHCl3 and [Ag(dppf)(phen)]ClO4(phen = 1,10-phenanthroline)

Addition of 1,1′-bis(diphenylphosphino)ferrocene (dppf) to a solution of AgClO4 in 1 : 1 molar ratio led to the complex [Ag(OClO3)(dppf)]1. Substitution of the perchlorate anion in 1 by monodentate ligands gave [Ag(dppf)(L)]ClO4(L = PPh32 or SPPh33), or with the less sterically demanding phosphine PPh2Me the four-co-ordinate silver(I) complex [Ag(dppf)(PPh2Me)2]ClO44. Direct reaction of dppf with [Ag(OClO3)(PPh3)] also affords complex 2. The homoleptic derivative [Ag(dppf)2]ClO45 can be synthesized by reaction of dppf and AgClO4 using a molar ratio of 2 : 1, or by substitution of the ClO4– by dppf in complex 1. Treatment of 1 with other bidentate ligands such as 1,10-phenanthroline (phen), 2,2′-bipyridine (bipy) or bis(diphenylphosphino)methane disulfide (SdppmS) gave mixed cationic four-co-ordinate complexes [Ag(dppf)(L–L)]ClO4(L–L = phen 6, bipy 7 or SdppmS 8); with sodium dithiocarbamates Na(S2CNR2) the neutral species [Ag(S2CNR2)(dppf)](R = Et 9 or Me 10) were obtained. The crystal structures of complexes 2, 5 and 6 have been established by X-ray diffraction. Compound 2 shows a trigonal-planar silver(I) centre, whereas in complexes 5 and 6 the silver atom exhibits a tetrahedral geometry.

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

An unprecedented η2-type interaction between the Au atoms and the cyclopentadienyl rings has been found in [Au2Cl2{Fc(S2CNEt2)2}] (shown), one of several gold(I) and gold(III) complexes with the 1,1′-bis(diethyldithiocarbamate)ferrocene ligand that are described. Their crystal structures are reported, together with that of Fc(S2CNEt2)2.

1,1′-Bis(diphenylthiophosphoryl)ferrocene as a trans- chelating ligand in gold(I) and silver(I) complexes

The reaction of 1,1′-bis(diphenylthiophosphoryl)ferrocene (dptpf) with AgClO4 or [Au(tht)2]CF3SO3(tht = tetrahydrothiophene) in a 1 : 1 molar ratio led to complexes of the stoichiometry [M(dptpf)]+ The crystal structures of both complexes revealed a linear co-ordination geometry with a novel trans co-ordination by the ligand.

1,1′-Bis(diphenylthiophosphoryl)ferrocene complexes of gold(I) and gold(III)

Abstract Linear and three-coordinate gold(I) complexes with the ferrocenyl derivative 1,1′-bis(diphenylthiophosphoryl)ferrocene (dptpf) of the type [(μ-dptpf)(AuX) 2 ] (X=Cl, 1 ; C 6 F 5 ), [(μ-dptpf)(AuPPh 3 ) 2 ](ClO 4 ) 2 or [Au(dptpf)(PPh 3 )]ClO 4 have been obtained. Oxidation of 1 with chlorine gave the mixed gold(I)–gold(III) compound [Au(dptpf)][AuCl 4 ]. The dinuclear gold(III) complexes [(μ-dptpf){Au(C 6 F 5 ) 3 } 2 ] or [(μ-dptpf){Au(C 6 F 5 ) 2 Cl} 2 ] were obtained from the corresponding gold precursors and dptpf. The crystal structures of [Au(dptpf)][AuCl 4 ] and [(μ-dptpf){Au(C 6 F 5 ) 2 Cl} 2 ] have been determined by X-ray diffraction studies.

1,1′-Bis(diphenyloxophosphoryl)ferrocene (dpopf) as ligand in silver(I) complexes. Crystal structure of [Ag(dpopf)(PPh3)2]ClO4

Abstract The ligand 1,1′-bis(diphenyloxophosphoryl)ferrocene, dpopf, reacted with silver derivatives to afford mononuclear complexes, [Ag(OClO3)(dpopf)] (1), [Ag(dpopf)2]ClO4, [Ag(dpopf)(PPh3)]ClO4, or the dinuclear complex, [{Ag(PPh3)}2(dpopf)](ClO4)2. From 1, other three-, [Ag(dpopf)(SPPh3)]ClO4, and four-coordinated derivatives, [Ag(dpopf)(PPh3)2]ClO4 (6) [Ag(dpopf)(LL)]ClO4 [LL=bipy, (SPPh2)2CH2] were obtained by substitution reactions. The crystal structure of 6 was solved and revealed the expected distorted tetrahedral coordination at silver, with a ligand bite angle of 96.10(13)°.

A double sandwich silver(I) polymer with 1,1′-bis(diethyldithiocarbamate)-ferrocene

The polymeric complex [Ag{Fc(S2CNEt2)2}]n[ClO4]n, in which the silver centres are bonded to two sulfur atoms of different ferrocene moieties and also to the cyclopentadienyl rings in an η2 fashion, is reported.

Co-ordination chemistry of 1,1′-bis(diphenylthiophosphoryl)ferrocene (dptpf) towards silver(I). Crystal structure of the polymeric complex [Ag2(µ-dptpf){(SPPh2)2CH2}2]n[ClO4]2n‡

The ligand 1,1′-bis(diphenylthiophosphoryl)ferrocene, dptpf, reacted with various silver complexes to afford two-, three- or four-co-ordinate species. Thus the reaction of dptpf with [Ag(OClO3)(PPh3)] in 1∶1 or 1∶2 molar ratio gave the three-co-ordinate [Ag(dptpf)(PPh3)]ClO4 or the linear [Ag2(dptpf)(PPh3)2][ClO4]2 derivatives. Similarly, the treatment of dptpf with AgClO4 in 2∶1 or 1∶1 molar ratio afforded the homoleptic compounds [Ag(dptpf)2]ClO4 or [Ag(dptpf)]ClO4; in the latter dptpf acts as a trans-chelating ligand. The complex [Ag(dptpf)]ClO4 can react further with bidentate ligands such as 2,2′-bipyridine (bipy) or bis(diphenylthiophosphoryl)methane, (SPPh2)2CH2, leading to the four-co-ordinate [Ag(dptpf)(bipy)]ClO4 or the four-co-ordinate polymeric species [Ag2(µ-dptpf){(SPPh2)2CH2}2]n[ClO4]2n, which was characterised by X-ray diffraction.