Synthesis, Structure, and Properties of a T-Shaped 14-Electron Stiboranyl-Gold Complex

Wade, Casey R.; Lin, Tzu‐Pin; Nelson, Raymond J.; Mader, Elizabeth A.; Miller, Jeffrey T.; Gabbaı̈, François P.

doi:10.1021/ja201092g

Cited by 77 publications

(61 citation statements)

References 88 publications

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“…The method was recently applied to show that a gold-antimony(V) complex, with a short Au-Sb contact (2.76 Å) framed by two 1,8-naphthalenediyl linkers, exhibits an aurate-stibonium character, and thus a Au -(I)→Sb + (V) (retro)dativity rather than a Au(III)-Sb(V) pure covalency [26]. 0.0007 Å) as expected for dative bonding [28].…”

Section: Experimental Characterization Of Dative Bondingmentioning

confidence: 99%

On the nature of the dative bond: Coordination to metals and beyond. The carbon case

Lepetit

Maraval

Canac

et al. 2016

Coordination Chemistry Reviews

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Section: Experimental Characterization Of Dative Bondingmentioning

confidence: 99%

On the nature of the dative bond: Coordination to metals and beyond. The carbon case

Lepetit

Maraval

Canac

et al. 2016

Coordination Chemistry Reviews

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“…Further inspection of the structure reveals a Au1-Sb1 separation of 2.8374(4 [12] and [Au(m 2 -1,8-(C 10 H 6 )) 2 SbPh 2 ] (2.76 av.). [13] Another noteworthy feature is the value of the Au1-Sb1-C37 angle (164.80 (11)8) which indicates that the stibine ligand approaches the gold atom to achieve a seesaw rather than a tetrahedral geometry.…”

mentioning

confidence: 99%

Two‐Electron Redox Chemistry and Reversible Umpolung of a Gold–Antimony Bond

Wade

Gabbaı̈

2011

Angew Chem Int Ed

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Two-electron redox processes occurring at the core of dinuclear metal complexes are important because of their implication in a number of chemical transformations ranging from the photocatalytic production of dihydrogen [1] to the oxidative functionalization of CÀH bonds.[2] Two-electron redox processes are also well documented for binuclear gold complexes [3] as well as for gold/rhodium, [4] gold/iridium [5] and gold/platinum [6] heterobimetallic complexes. One of the common features displayed by all of these complexes relates to their ability to sustain two-electron redox chemistry without decomposition of the bimetallic core. As part of our interest in fundamental aspects of main-group chemistry, we have recently questioned whether similar processes could also be observed at the bimetallic core of main-group/transitionmetal complexes.Triarylstibines are soft s-donor ligands which have been incorporated in a variety of late transition-metal complexes. [7] They are also well known to undergo facile two-electron oxidation when exposed to oxidizing agents such as halogens.[8] While there is precedent for dialkylstibido transitionmetal compounds (type A) to undergo oxidative addition at the antimony center, [9] no analogous reactivity has been reported for stibine metal complexes of type B. With the discovery of main-group-based, two-electron redox platforms in mind, we have now decided to study the synthesis and oxidation of complexes of type B. Herein, we report the first incarnation of this idea in the case of a gold-antimony compound.To prevent dissociation of the gold-antimony bimetallic core upon oxidation, we chose to work with a stibine ligand whose interaction with the gold center would be supported by pendant donor ligands. These considerations led us to focus on the triphosphanylstibine ligand [(o-(Ph 2 P)C 6 H 4 ) 3 Sb] (referred to as L) [10] which was allowed to react with [AuCl(tht)] in CH 2 Cl 2 /acetone to produce 1-Cl as a pale yellow precipitate (Scheme 1). At À55 8C in CDCl 3 , the 31 P{ 1 H} NMR spectrum of 1-Cl displays two signals at d = + 39.5 and À7.4 ppm in a 2:1 intensity ratio thus suggesting that only two of the three phosphine arms of the ligand are coordinated to the gold atom. Upon elevation of the temperature, these two peaks coalesce into one signal at d = + 24.4 ppm indicating the onset of a rapid exchange. Line shape analysis of the 31 P{ 1 H} NMR spectra of 1-Cl over the À55 8C-+ 22 8C temperature range followed by an Eyring analysis afforded DH°= + 16.7 (AE 0.9) kcal mol À1 and DS°= + 16.6(AE3.8) cal mol À11 K À11 , suggesting a dissociative exchange of the phosphine arms. The ESI mass spectrum of this complex shows a peak at m/z 1101.1180 amu corresponding to the [LAu] + ion. A final clarification of the structure of this compound was derived from a single-crystal diffraction study which confirmed the coordination of two of the phosphorus atoms to the gold chloride fragment (Figure 1).[11] Inspection of the P-Au-P and P-Au-Cl angles (AE = 359.468) shows that these prim...

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“…49 And this strong interaction between Au and Sb atoms can also be supported by a comparison of its isoelectronic mercury analogue. 50 Indeed, despite the similarity of the covalent radii of mercury (1.32 Å) and gold (1.36 Å), 38 the Au-Sb contact (2.641 Å-2.661 Å) is markedly shorter than the Hg→Sb bond (3.06 Å). Further inspiration these structures reflect a Sb-Sb bond in the range from 2.783 Å to 2.884 Å.…”

Section: Resultsmentioning

confidence: 99%

Computational insights into the concomitant changes of hollow interior evolution in [SbnAunSbn]m (n=3, 4, 5, 6; m= -3, -2, -1, -2) complex

et al. 2017

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A series of novel all-metal sandwich species, [SbnAunSbn]m (n= 3, 4, 5, 6; m= -3, -2, -1, -2), are carefully designed and are systematically investigated in term of structure, bonding nature, stability, and potential application. These results show that [SbnAunSbn]m (n=3, 4, 5, 6; m= -3, -2, -1, -2), have local minimum values on their potential energy surfaces. For the Sb-Sb and Sb-Au bond, they are obviously covalent features, while in Au-Au, there is a typical aurophilic interaction. Furthermore, these species present expected stability owing to the positive dissociation energy, great Egap, ionization potential (IP), aromaticity and perfected mechanical stability. Interestingly, [Sb5Au5Sb5]- and [Sb6Au6Sb6]2- are aromatic, while both [Sb3Au3Sb3]3- and [Sb4Au4Sb4]2- possess conflicting aromaticity. And all the title species hold tube aromaticty and δ aromaticty. prediction The application suggests that the Sb site is favorable for absorbing CO in the units, and [Sb3Au3Sb3]3- is more suitable than others; CO is absorbed by the p-p interaction between the C and Sb atoms.

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Synthesis, Structure, and Properties of a T-Shaped 14-Electron Stiboranyl-Gold Complex

Cited by 77 publications

References 88 publications

On the nature of the dative bond: Coordination to metals and beyond. The carbon case

On the nature of the dative bond: Coordination to metals and beyond. The carbon case

Two‐Electron Redox Chemistry and Reversible Umpolung of a Gold–Antimony Bond

Computational insights into the concomitant changes of hollow interior evolution in [SbnAunSbn]m (n=3, 4, 5, 6; m= -3, -2, -1, -2) complex

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