14243-58-4Relevant academic research and scientific papers
Synthesis, X-ray molecular structure analysis, and study on ligand scrambling reactions of new thiolatogold(I) complexes with various phosphines
Onaka, Satoru,Katsukawa, Yoshitaka,Shiotsuka, Michito,Kanegawa, Osamu,Yamashita, Masahiro
, p. 100 - 110 (2008/10/08)
Treatment of Au(PPh3)Cl, (AuCl)2(trans-dpen) and (AuCl)2(dppfe) with Sn(SPh)(n-Bu)3 and/or PhSH/KOH affords Au(PPh3)(SPh) (1), (AuSPh)2(μ-trans-dpen) (2), (AuSPh)2(μ-dppfe) (3), (AuSPh)(μ-t
Luminescence Studies of Gold(I) Thiolate Complexes
Forward, Jennifer M.,Bohmann, David,Fackler, John P. Jr.,Staples, Richard J.
, p. 6330 - 6336 (2008/10/08)
A series of monomeric gold(I) complexes containing phosphine and thiolate ligands have been synthesized. The two phosphines used were triphenylphosphine and the 1,3,5-triaza-7-phosphaadamantanetriylphosphine (TPA). Substituted benzenethiolate ligands were used with the substituent in either the ortho, meta or para position. All of the compounds synthesized luminesce at 77 K in the solid state, where the excitation is assigned to a ligand to metal charge transfer (LMCT) transition from the sulfur ofthe thiolate ligand to the gold center. The large Stokes shifts and long lifetimes measured imply that the emission is phosphorescence. The position of the emission maxima can be affected by both the substituents onthe thiolate ligand and the presence of gold-gold interactions between neighboring molecules in the solid state. Four of these compounds have been structurally characterized. Compound 3 crystallizes in the triclinicspace group P1- (No. 2) with cell constants a = 8.641(2) ?, b = 11.423(2) ?, c = 12.118(2) ?, α = 103.36(3)°, β =99.34(3)°, γ = 105.95(3)°, and Z = 2. Refinement of2861 reflections and 253 parameters yields R = 0.0275 and Rw = 0.0669. Compound 4 crystallizes in the orthorhombic space group P212121 (No. 19)with cell constants a = 6.3100(10) ?, b = 12.127(3) ?, c = 18.193(3) ?, and Z = 4. Refinement of 1231 reflections and 163 parameters yields R = 0.0292 and Rw = 0.0360. Compound 5 crystallizes in the monoclinic space group P21/n (No. 14) with cell constants a = 12.252(3) ?, b = 17.002(6) ?, c = 22.845(4) ?, β = 91.25(2)°, and Z = 12. Refinement of 5534 reflections and 541 parameters yields R =0.0698 and Rw = 0.0786. Compound 10 crystallizes in the monoclinic space group C2/c (No. 15) with cell constants a = 17.542(5) ?, b = 18.831(6) ?, c = 11.647(4) ?, β = 119.52(2)°, and Z = 8. Refinement of 2207 reflections and 181 parameters yields R = 0.0327 and Rw = 0.0441.
Preparation and Crystal Structures of Gold(I) Complexes of a Series of Benzenethiolates: Pair Formation by Gold-to-Gold Interactions of (Benzenethiolato)(triphenylphosphane)gold(I)
Nakamoto, Masami,Hiller, Wolfgang,Schmidbaur, Hubert
, p. 605 - 610 (2007/10/02)
Chloro(triphenylphosphane)gold(I) reacts readily with benzenethiol C6H5SH and a series of sterically hindered (2,4,6-trialkylbenzene)thiols 2,4,6-R3C6H2SH in the presence of NEt3 to yield stable gold(I) complexes Ph3PAu(S-2,4,6-C6H2R3) .The crystal structures of these complexes have been determined by single-crystal X-ray diffraction analysis.In all compounds the gold atoms are linearly two-coordinate with very similar bond lengths and angles. - While complexes 2-4 with bulky thiolate ligands are monomeric in the crystal lattice, complex 1 has been found to form pairs of molecules with intermolecular gold-gold contacts of 313.5(5) pm.The Moessbauer spectra of the complexes exhibit large isomer shifts (I.S.), ranging from 3.06 to 3.72 mm s-1, and quadrupole splittings (Q.S.), ranging from 7.90 to 8.68 mm s-1.These data can be attributed to the strong electron-donating properties of the benzenethiolate ligands.The gold-gold contacts in complex 1 lead to I.S. and Q.S. values which are slightly smaller than those of 2-4.The Au-S distances do not show a major influence of the S-Au-P pairing in complex 1 as compared to complexes 2-4. Key Words: Gold(I) complexes/Gold(I) thiolates/Thiolato complexes.
