The Structural Chemistry of GoId(I) Quinoline-2-thiolate and Iodide Complexes of Polytertiary Phosphines

Abstract

Treatment of (chloro)gold(I) complexes of di-and tetra-tertiary phosphines with equivalent quantities of sodium quinoline-2-thiolate in methanol / dichloromethane affords the correspond ing (phosphine)gold(I) quinoline-2-thiolates in high yields. The di-and tetranuclear complexes, respectively, of a,u>bis(diphenylphosphino)-propane (1), -butane (2) and -pentane (3) and of tris(2-diphenylphosphino-ethyl)phosphine (4) have been obtained as crystalline solids, and the structures of 2 and 4 have been determined by single crystal X-ray diffraction studies. Un expectedly, the molecules of 2 are loosely aggregated into strings via weak intermolecular gold-sulfur, not via Au-Au interactions. Compound 4 is a monomeric tetranuclear cluster in the solid state with two intramolecular gold-gold bonds. Bis(2-diphenylphosphino-ethyl)-phenylphosphine (PPP) forms trinuclear complexes with gold(I) chloride, bromide and iodide (5a -c). The iodide complex features a chain structure through intermolecular Au -Au contacts between the two terminal P-Au-I units. The closest contacts between the chains are determined by Au-I and I -I interactions of the central P-Au-I unit.

Luminescent Phosphine Gold(I) Thiolates: Correlation between Crystal Structure and Photoluminescent Properties in [R3PAu{SC(OMe)NC6H4NO2-4}] (R = Et, Cy, Ph) and [(Ph2P-R-PPh2){AuSC(OMe)NC6H4NO2-4}2] (R = CH2, (CH2)2, (CH2)3, (CH2)4, Fc)

“…It is likely that, for the shorter (CH 2 ) n bridges between the phosphorus atoms, the Au···Au interactions are able to stabilize the syn conformation, but beyond the n = 3 threshold, intramolecular Au···Au interactions are not found. Indeed, all of the known [{Ph 2 P(CH 2 ) 2 PPh 2 }{Au(SR)} 2 ] structures − feature a similar anti conformation, and only in two structures are intermolecular Au···Au interactions found. , It is clear that, generally, syn conformations are rare in dppb complexes involving gold, with the notable exception being found in the structure of [{Ph 2 P(CH 2 ) 4 PPh 2 }(AuCl) 2 ], in which an approximate syn arrangement is stabilized by intermolecular Au···Cl interactions provided by a solvent dichloromethane molecule . In the case of 7 , it is likely that intermolecular aurophilic interactions are precluded because of the size of the thiolate ligand combined with the presence of the intramolecular Au···O interactions that serve to reduce the residual Lewis acidity of the gold centers.…”

Supramolecular aggregation patterns in the crystal structures of the dinuclear phosphinegold(i) thiolates, [(Ph2P(CH2)4PPh2){AuSC(OR)NC6H4Y-4}2] for R = Me, Et or iPr and Y = H, NO2or Me: the influence on intermolecular interactions exerted by R and Y

“…It turns out that in all but one of the known structures with general formula [{Ph 2 P(CH 2 ) 4 PPh 2 }{Au(SR)} 2 ] a similar anti-conformation is found. [14][15][16][17] syn-Conformations are rare in dppb complexes involving gold, with the notable exception being found in the structure of [{Ph 2 P(CH 2 ) 4 PPh 2 }(AuCl) 2 ].CH 2 Cl 2 in which an approximate syn-arrangement is stabilized by intermolecular Au … Cl interactions provided by the solvent dichloromethane. 18 Of the structures having an anti-conformation, in only two, i.e.…”

Observation of a P/M interconversion of a gold–phosphine helicate via   31P NMR

“…It is interesting to note that the related compound [Au 3 (m-pp 2 )I 3 ] as well as the Au(III) complex [Au(C 6 F 5 ) 3 ] 3 (pp 2 ), both with the ligand+Au ratio of 1+3, do not show any helical suprastructures. 5 The 31 P NMR pattern of 1 in MeOH at 333 K consists of an [A 2 X] 2 pattern; at 213 K an [AMX] 2 spin system is observed in keeping with a C2 symmetry of the complex cation. 6 The coalescence temperature is 260 K, corresponding to a DG ‡ of 46 kJ.…”