Gold complexes with phosphines

Recently, several mono and dinuclear gold complexes with phosphine or phosphite ligands have been screened for anticancer activity and good in vitro activity equal or superior to cisplatin was reported [48-51]. 

Other complexes with phosphine sulfides are the three coordinate [Au (S-PPh2)2C(PPh2S) (PPh2Bun)],302 the /i4-phospha-l-thiethane compound [Fe3(CO)9(/i4-PS)(AuPPh3)2] (558),3 27 and the gold(I) dendrimers containing P=NP=NP=S or P=NP=S groups as (559).3028... 

COMPLEXES OF GOLD(III) WITH PHOSPHINE AND ARSINE AND STBINE LIGANDS 897... 

Homoleptic Gold(I) Complexes with Phosphine Ligands. 272... 

COMPLEXES OF GOLD(m) WITH PHOSPHINE, ARSINE AND SHRINE LIGANDS... 

The use of gold complexes with chiral phosphines to promote asymmetric cyclization reactions remains the most studied approach of several groups.However, Toste and coworkers pushed this chemistry further, when they combined the additive elfects of a chiral phosphine ligand and a chiral counter ion which forms an ion pair with the active species [L Au] X 3> (L = chiral phosphine ligand X = chiral counter ion). Thus a dramatic increase in Au(I)-catalysed enantioselective intramolecular hydroalkylation of... 

Apart from these findings, Echavarren and coworkers found a different strategy to isolate catalytically active gold(l) phosphine and NHC complexes [25]. They were able to isolate an array of different cationic gold complexes with noncoordinating anions, typically SbFs , which bear a nitrile ligand (see Scheme 9.9). 

Three mixed ligand complexes of gold(Il) with phosphines and selenones, [Et3PauSe=C]Br as analogues of auranofin (EtsPAuSR) have been prepared and characterised by elemental analysis, IR and NMR methods. solid-state NMR showed the chemical shift difference between free and bound selenone to gold(l). Se NMR chemical shifts (55 ppm) upon complexation in the solid state indicated stability. ... 

Gold complexes with A -heterocyclic carbenes (NHC) [34—37], such as 11-13 [16, 30, 38 2], cationic 14-16[43, 44] as well as neutral 17 and 18 [45, 46], usually afford more selective catalysts, due to the more donating ability of the NHC in comparison with phosphine ligands. Gold hydroxo complex [Au(IPr)OH] can also be used as catalyst by activation with a Brpnsted acid [47, 48]. Acyclic carbenes [49-53], such as 21, and other related carbenes [54-58] also give rise to selective catalysts of moderate electrophilicity. 

Other cases of transition-metal ion binding to the imidazole ring N9 atom of the purine ligand have been reported in the monomer [TiCl(cp)2(pur-KA )] (cp is the cyclopentadienyl anion) with a purinate monoanion" and a series of neutral dinuclear and mononuclear gold(I) complexes with phosphine and purin-9-ate synthesized under basic conditions. There are reported examples of Mn(II) binding to N donor sites of nueleobases in biopolymeric systems, but coordinative Mn-N linkages involving isolated nueleobases, as seen in... 

The soft Au+ forms relatively few complexes compared with those of phosphines. Complexes with ammines, nitriles and diazoles like Au(NH3)2 and Au(RCN)2 are known but little studied. In linear Au(NH3)2, Au-N is 2.01-2.03 A [70a], [Au(NCPh)2]+ has been used as a labile source of other gold complexes [70b]. AuCl(piperidine) is a monomer with weak tetra-meric association in contrast AuX(py) (X = Cl, Br, I) are [Aupy2]+[AuX2] with a chain structure in the solid state (and Au-Au interactions), suggesting a close balance between factors for molecular and ionic structures [70c] (note also the tetrahydrothiophene complexes in section 4.10.6). 

B. (2000) Gold and Silver Complexes with the Ferrocenyl Phosphine FcCH2PPh2 [Fc = (Tl5-C5H5)Fe(h5-C5H4)]. Inorganic Chemistry, 39(4), 680-687. 

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