Cycloaurated complexes of aryl carbanions: Digold(I), Digold(II) and beyond

Mirzadeh, Nedaossadat; Bennett, Martin A.; Bhargava, Suresh K.

doi:10.1016/j.ccr.2013.02.011

Cited by 40 publications

(35 citation statements)

References 83 publications

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“…Aurophilicity and photoluminescence are two intimately related features in organogold chemistry . The judicious choice of multi‐dentate ligands is often crucial for the observation of aurophilic interactions that not only exist in the solid‐state, but are also maintained in solution . peri ‐Substituted scaffolds, such as 1,8‐disubstituted naphthalenes and 5,6‐disubstituted acenaphthenes, are powerful building blocks to invoke non‐covalent, through‐space interactions between two molecular entities .…”

Section: Introductionmentioning

confidence: 72%

Aurophilicity and Photoluminescence of (6‐Diphenylpnicogenoacenaphth‐5‐yl)gold Compounds

et al. 2019

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The organotin precursors 6-Br-Ace-5-SnBu 3 (6, Ace = acenaphthyl) and 6-Ph 2 E-Ace-5-SnBu 3 (7a: E = P; 7b: E = As; 7c: E = Sb) were prepared and used for the synthesis of organogold complexes, namely, the homodinuclear arylgold(I) species (6-Ph 2 E-Ace-5-Au) 2 (8a: E = P; 8b: E = As; 8c: E = Sb), arylgold(III) dichloride 6-Ph 2 P-Ace-5-AuCl 2 (9), diarylgold(III) chloride [trans-(6-Ph 2 P-Ace-5-) 2 Au]Cl ([10]Cl), as well as the heterodinuclear gold complexes 6-Ph 2 P(AuX)-Ace-5-Au(AsPh 3 ) (11a: X = Cl; 11b: X = Br). Compounds 8a -8c, 11a, and 11b show significant aurophilic interactions, which are related to their photolumines- [a] naphth-5-yl)mercury and inorganic gold salts. [9] Due to the kinetic instability of the reported Hg-Au complexes, the formation of the cis-bis(6-diphenylphosphinoacenaphth-5-yl)gold cation [5] + was observed (Scheme 1). We now report on a series of peri-substituted (6-diphenylpnicogenoacenaphth-5-yl)gold compounds, which show substantial aurophilic interactions as well as green-yellow photoluminescence in solution and, in some cases, also in the solid state. These compounds were characterized by NMR, UV/Vis, and photoluminescence spectroscopy as well as X-ray crystallography. In addition, the aurophilic interactions and photoluminescence properties were characterized theoretically employing density functional theory (DFT) and time-dependent density functional theory (TD-DFT). Determination of a set of real-space bonding indicators (RSBIs), derived from the electron density (ED), facilitates straight-forward characterization of chemical bonds in complex molecular systems. The wide-spread topological approach according to the Atoms-In-Molecules (AIM [10] ) space-partitioning provides atomic properties, such as charges and volumes, a distinct bond paths motif, as well as bond properties, which are used to analyze various kinds of chemical interactions. [11] A recent approach relies on the reduced density gradient, s(r) = [1/2-(3π 2 ) 1/3 ]|∇ρ|/ρ 4/3 , which is displayed in a way to uncover regions in space where non-covalent interactions (NCI [12] ) occur. By mapping the ED times the sign of the second eigenvalue of the Hessian [sign(λ 2 )ρ] on iso-surfaces of s(r), different contact types including steric/repulsive (λ 2 > 0), van der Waals-like (λ 2 ≈ 0), and attractive (λ 2 < 0) interactions can be assigned. In complementary fashion, the computed electron pair densities may be analyzed according to the topological Electron Localizability Indicator (ELI-D [13] ) method, which divides real-space into basins of localized electron pairs. By applying this tool, which provides electron populations of bonds and lone-pairs, effects of electron redistribution due to subtle structural changes become visible. As shown in previous studies, the combined use of AIM, NCI, and ELI-D is superior to the restriction to one type of RSBI as different aspects of atom-atom interactions (bond Scheme 2. Synthesis of the organotin precursors 6 and 7a -7c. 648 polarities, degree of covalency, etc.) may be...

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Section: Introductionmentioning

confidence: 72%

Aurophilicity and Photoluminescence of (6‐Diphenylpnicogenoacenaphth‐5‐yl)gold Compounds

et al. 2019

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“…Continuing our research into the development of gold complexes [9] for the treatment of cancer, [10][11][12][13][14][15] and inspired by the promising results obtained with complexes containing iminophosphorane ligands, we were interested in preparing cycloaurated compounds containing closelyr elated phosphine sulfide ligands. The monocyclic gold(III) compounds [AuCl 2 {k 2 -2-C 6 H 4 P(S)R 2 }] (R = Ph, NEt 2 )h ave been reported, from which the thiosalicylate derivative, [Au(1,2-SC 6 H 4 CO 2 ){k 2 -2-C 6 H 4 P(S)NEt 2 }],w as synthesized.…”

Section: Introductionmentioning

confidence: 99%

Potent and Selective Cytotoxic and Anti‐inflammatory Gold(III) Compounds Containing Cyclometalated Phosphine Sulfide Ligands

Reddy

Pooja

Privér

et al. 2019

Chemistry A European J

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Four cycloaurated phosphine sulfide complexes, [Au{k 2 -2-C 6 H 4 P(S)Ph 2 } 2 ][AuX 2 ][ X = Cl (2), Br (3), I( 4)] and [Au{k 2 -2-C 6 H 4 P(S)Ph 2 } 2 ]PF 6 (5), have been prepared and thoroughly characterized. The compounds were found to be stable under physiological-like conditions and showede xcellent cytotoxicity against ab road range of cancerc ell lines and remarkable cytotoxicity in 3D tumor spheroids. Mechanistic studies with cervical cancer( HeLa) cells indicated that the cytotoxic effects of the compounds involve the inhibition of thioredoxin reductasea nd induction of apoptosis through mitochondrial disruption. In vivo experiments in nude mice bearing HeLa xenografts showedt hat treatment with compounds 4 and 5 resulted in significant inhibition of tumorg rowth (35.8 and 46.9 %, respectively), better than that of cisplatin (29 %). The newly synthesized gold complexesw ere also evaluated for their in vitro and in vivo antiinflammatory activity through the study of lipopolysaccharide (LPS)-activated macrophages and carrageenan-induced hind paw edemainr ats, respectively.

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“…Given our background in the synthesis of organogold complexes,34 we were interested to design and prepare flavonoid derivatives of gold(I)–phosphine compounds, binding together two potentially anticancer‐active components (namely a gold–phosphine and a flavonoid) through a gold–carbon σ‐bond. Several factors were considered when designing these compounds, one being the introduction of a chlorine substituent into the phenyl ring of the flavone moiety, which has been shown to improve the cytotoxicity of flavone‐based drugs 35.…”

Section: Introductionmentioning

confidence: 99%

Linking Flavonoids to Gold – A New Family of Gold Compounds for Potential Therapeutic Applications

et al. 2015

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Cycloaurated complexes of aryl carbanions: Digold(I), Digold(II) and beyond

Cited by 40 publications

References 83 publications

Aurophilicity and Photoluminescence of (6‐Diphenylpnicogenoacenaphth‐5‐yl)gold Compounds

Aurophilicity and Photoluminescence of (6‐Diphenylpnicogenoacenaphth‐5‐yl)gold Compounds

Potent and Selective Cytotoxic and Anti‐inflammatory Gold(III) Compounds Containing Cyclometalated Phosphine Sulfide Ligands

Linking Flavonoids to Gold – A New Family of Gold Compounds for Potential Therapeutic Applications

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