316802-86-5Relevant academic research and scientific papers
A gold(I) mononuclear complex and its association into binuclear and cluster compounds by hydrogen bonding or metal ion coordination
Hao,Mansour,Lachicotte,Gysling,Eisenberg
, p. 5520 - 5529 (2000)
The mononuclear Au(I) complex, Au(Spy)(PPh2py) (1), has been synthesized and characterized structurally. The complex possesses the expected linear coordination geometry with a S-Au-P bond angle of 176.03(6)° and no evidence of aurophilic interactions between nearest neighbor Au(I) ions in the solid state. Protonation of the pendant pyridyl groups of 1 leads to the formation of the H-bonded dimer [{Au(SpyH)(PPh2py)}2](PF6)2 (2), which has also been structurally characterized. A linear coordination geometry at the Au(I) ions in 2 with a S-Au-P bond angle of 173.7(2)° is augmented by evidence of a strong aurophilic interaction with a Au···Au distance of 2.979(1) A. The pendant pyridyl groups of 1 have also been used to bind Cu(I) by reactions with [Cu(NCMe)4](PF6) and Cu(P(p-tolyl)3)2(NO3) leading to the formation of the heterobimetallic complexes [{AuCu-(μ-Spy)(μ-PPh2py)}2] (PF6)2 (3) and [AuCu(P(p-tolyl)3)2(μ-Spy) (μ-PPh2py)](NO3) (4), respectively. A structure determination of 3 reveals a tetranuclear complex composed of two AuCu(μ-Spy)(μ-PPh2py)+ units held together by bridging thiolate ligands. A strong metal-metal interaction is noted between the two different d10 ions with nearest Au-Cu distances averaging 2.6395 A. The S-Au-P bond angles in 3 deviate slightly from linearity due to the Au···Cu interactions, while the coordination geometries at Cu(I) are distorted tetrahedral consisting of the two pyridyl nitrogen atoms, a bridging thiolate sulfur, and the interacting Au(I) ion. While mononuclear complex 1 is only weakly emissive in the solid state and in fluid solution, complexes 2-4 show stronger photoluminescence in the solid state and rigid media at 77 K, and in fluid solution. The emission maxima for 2-4 in ambient temperature fluid solution are 470, 635, and 510 nm, respectively. A tentative assignment of the emitting state as a S(pπ) → Au LMCT transition is made on the basis of previous studies of Au(I) thiolate phosphine complexes. Shifts of λem result from the influence of H bonding or Cu(I) coordination on the filled thiolate orbital energy, or on the effect of metal-metal interaction on the Au(I) acceptor orbital energy. Crystal data for Au(Spy)(PPh2py) (1): triclinic, space group P1 (No. 2), with a = 8.3975(4) A, b = 11.0237(5) A, c = 12.4105(6) A, α = 98.6740(10)°, β = 105.3540(10)°, γ = 110.9620(10)°, V = 995.33(8) A3, Z = 2, R1 = 3.66% (I > 2σ(I)), wR2 = 9.04% (I > 2σ(I)) for 2617 unique reflections. Crystal data for [{Au(SpyH)(PPh2py)}2](PF6)2 (2): triclinic, space group P1 (No. 2), with a = 14.0284(3) A, b = 14.1093(3) A, c = 15.7027(2) A, α = 97.1870(10)°, β = 96.5310(10)°, γ = 117.1420(10)°, V = 2692.21(9) A3, Z = 2, R1 = 7.72% (I > 2σ(I)), wR2 = 15.34% (I > 2σ(I) for 5596 unique reflections. Crystal data for [{AuCu(μ-Spy)(μ-PPh2py)}2] (PF6)2 (3): monoclinic, space group P21/c (No. 14), with a = 19.6388(6) A, b = 16.3788(4) A, c = 17.2294(5) A, β = 91.48°, V = 5540.2(3) A3, Z = 4, R1 = 3.99% (I > 2σ(I)), wR2 = 8.38% (I > 2σ(I)) for 10597 unique reflections.
Synthesis and biological evaluation of thiolate gold(i) complexes as thioredoxin reductase (TrxR) and glutathione reductase (GR) inhibitors
Fereidoonnezhad, Masood,Ahmadi Mirsadeghi, Hasti,Abedanzadeh, Sedigheh,Yazdani, Alireza,Alamdarlou, Arsalan,Babaghasabha, Mojgan,Almansaf, Zainab,Faghih, Zeinab,McConnell, Zachary,Shahsavari, Hamid R.,Beyzavi, M. Hassan
, p. 13173 - 13182 (2019)
New gold(i) thiolate complexes [(PPh2py)Au(SR)] (PPh2py = 2-(diphenylphosphino)pyridine and SR = the deprotonated form of pyridine-2-thiol (HSpy, 1a), pyrimidine-2 thiol (HSpyN, 1b), benzothiazole-2-thiol (HSbt, 1c) and 2-thiazoline-2-thiol (HSt, 1d)) were prepared by the reaction of chloro gold complex [(PPh2py)AuCl], A, with the corresponding in situ generated thiolate salt (through a nucleophilic substitution reaction) under inert conditions. All complexes are characterized by NMR spectroscopy and the structures of 1b and 1d were further identified by single crystal X-ray determination. An in vitro cytotoxicity evaluation against five human cancer cell lines including A549 (nonsmall cell lung cancer), SKOV3 (human ovarian cancer), MCF-7 (human breast cancer), SW1116 (colon cancer) and HeLa (cervical cancer) demonstrated the promising antitumor effects of 1b in comparison with standard auranofin and cisplatin. The effects of these compounds on the proliferation of non-tumoral breast cell line MCF-12A showed good selectivity among tumorigenic and non-tumorigenic cell lines. The results illustrated that 1b effectively produces cell death by inducing apoptosis in the MCF-7 human breast cancer cell line. These complexes inhibit both cytosolic (TrxR1) and mitochondrial (TrxR2) thioredoxin reductases as well as glutathione reductase (GR).
