Dinuclear Complexes of Gold(<scp>I</scp>) Containing Bridging Cyclometalated Arylphosphane or Arylarsane Ligands

Bennett, Martin A.; Bhargava, Suresh K.; Griffiths, Kieran; Robertson, G. B.; Wickramasinghe, W. A.; Willis, Anthony C.

doi:10.1002/anie.198702581

Cited by 60 publications

(37 citation statements)

References 13 publications

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“…All three compounds 8a ‐ 8c show the characteristics of repulsive peri ‐interactions as, e.g., long E1–Au1 peri ‐distances [3.1189(1) Å ( 8c ) to 3.3725(5) Å ( 8a )], large splay angles [14.6(5)° ( 8c ) to 22.3(4)° ( 8a )], as well as large out‐of‐plane displacements of the Au1 atoms [0.1758(1) Å ( 8a ) to 0.2683(1) Å ( 8c )], which might be caused by the close E1–Au1a distances of 2.2945(4) Å ( 8a ), 2.4072(2) Å ( 8b ), and 2.5675(1) Å ( 8c ), respectively. The Au–Au distances in 8a of 2.8142(2) Å and 8b of 2.9131(2) Å are very similar to the directly related compounds (2‐Ph 2 P‐C 6 H 4 ‐1‐Au) 2 {2.8594(3) Å}, [Au 2 {(C 6 H 3 ‐6‐Me)PPh 2 } 2 ] {2.861(2) Å}, and (2‐Ph 2 As‐C 6 H 4 ‐1‐Au) 2 {2.9358(5) Å} . The Au–Au distance in the heavier Sb analogue 8c of 3.0822(1) Å is slightly longer but still in the range of attractive aurophilic interactions .…”

Section: Resultsmentioning

confidence: 99%

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: Resultsmentioning

confidence: 99%

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

et al. 2019

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“…As ar esult of a slight twist of the bridgingl igands, the Au···Au separation in 1 [2.8664(3) ]i ss ignificantly smaller than that in the structurally similar complex [Au 2 (m-2-C 6 H 4 CH 2 PPh 2 ) 2 ][ 3.0035(9) ], [17] and more closely resembles the Au···Au separation in the eightmembered ring complex [Au 2 (m-2-C 6 H 4 PPh 2 ) 2 ][ 2.8594 (3) ]. [18] The oxidative addition of Cl 2 (as PhICl 2 ), Br 2 ,o rI 2 to 1 afforded the ionic gold(I)-gold(III) complexes[ Au{k 2 -2-C 6 H 4 P(S)Ph 2 } 2 ] [AuX 2 ][ X= Cl (2), Br (3), I( 4)] in yields of 80-90 %( Scheme 2). Complexes 2-4 each showed as inglet resonance at d = 56 ppm in their 31 PNMR spectra, comparable to that observed for [AuCl 2 {k 2 -2-C 6 H 4 P(S)Ph 2 } 2 ], [16] and ap eak at m/z = 783.08 in their mass spectra, which corresponds to the [Au{k 2 -2-C 6 H 4 P(S)Ph 2 } 2 ] + fragment (see FiguresS4-S14 in the Supporting Information).…”

Section: Chemistrymentioning

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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“…Ab initio HF/II and MP2/II calculations have been performed in order to analyze the metallophilic attraction in both complexes [314]. A head to tail arrangement is also observed in [Au 2 (ER 2 -R 0 -C 6 H 3 ) 2 ] (Figure 2.59) (E ¼ P, As, R ¼ Ph, Et, R 0 ¼ H; E ¼ As, R ¼ Ph; R 0 ¼ Me) [315][316][317].…”

Section: Complexes With Bridging Bidentate Ligandsmentioning

confidence: 99%

Gold–Gold Interactions

Crespo

2008

Modern Supramolecular Gold Chemistry

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This chapter focuses mainly on closed shell gold(I) atoms which are found to feel attraction among themselves. This attraction is able to modify expected geometries or support one-, two-or three-dimensional arrays and also leads to interesting properties. Closed shell metal cations are expected to repel each other. Nevertheless, an important number of examples containing [d 8 -d 10 -s 2 ] interactions are known. Particularly strong evidence has been accumulated on the attraction between two or more d 10 shells. In the case of gold(I) such attraction between two or more monovalent gold(I) ions in compounds has been observed structurally for a long time. In these situations the gold centers approach each other to a distance of between 2.7 and 3.3 Å. This range includes the distance between gold atoms in gold metal and approaches, or even overlaps with the range of distances found in the few real Au-Au single bonds. Schmidbaur coined the name aurophilic attraction in 1990 and defined it as the unprecedented affinity between gold atoms even with closed-shell electronic configurations and equivalent electrical charges [1]. Since that moment, aurophilicity has become one of the hot topics in gold chemistry, at first with the aim of understanding such interaction, more recently because of the observation that it may play an important role in interesting properties, thus understanding and modulating aurophilic interactions could help to govern these properties, which include the optical behavior. Although different origins are possible for the luminescent emissions of coordination complexes, such as intraligand transitions (ILT), ligand to metal or metal to ligand charge transfer transitions (LMCT, MLCT) and metal centered (MCT) transitions, in many luminescent gold complexes the emissions have been related to the presence of aurophilic interactions.Information about aurophilicity and chemical situations in which it is observed may be found in different works that may be classified as those which analyse closed shell interactions in general [2], those focused on aurophilicity [1,3], and others which analyze the role of these interactions in coordination [4] and organometallic gold Modern Supramolecular Gold Chemistry: Gold-Metal Interactions and Applications. Edited by Antonio Laguna

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Dinuclear Complexes of Gold(I) Containing Bridging Cyclometalated Arylphosphane or Arylarsane Ligands

Abstract: For corrigendum see DOI:10.1002/anie.198805891

Cited by 60 publications

References 13 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

Gold–Gold Interactions

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