Syntheses, structures and intermolecular interactions of tetraorganoammonium, -phosphonium and -stibonium dimethyl- and diphenyltetrahaloantimonates

Breunig, H. J.; Koehne, Tim; Moldovan, Ovidiu; Preda, Ana Maria; Silvestru, Anca; Silvestru, Cristian; Varga, Richard A.; Piedra-Garza, Luis Fernando; Kortz, Ulrich

doi:10.1016/j.jorganchem.2010.02.016

Cited by 12 publications

(3 citation statements)

References 25 publications

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“…Introduction of a Lewis acidic main group ligand in the coordination sphere of a transition metal is emerging as a powerful tool to control and sometimes enhance the catalytic reactivity of the transition metal center . While extensive efforts have been devoted to complexes featuring group 13 and 14 elements, recent advances in the Lewis acid chemistry of group 15 compounds led us to speculate that ligands featuring heavy pnictogens may present new opportunities for the exploration of synergistic effects between a transition metal center and a main group Lewis acid. As part of these efforts, we discovered that stibine ligands could be oxidized within the coordination sphere of a metal to afford metal–stiborane complexes in which the stiborane functions as a Z-type ligand .…”

Section: Introductionmentioning

confidence: 99%

T-Shaped Gold→Stiborane Complexes as Carbophilic Catalysts: Influence of the Peripheral Substituents

Sen

Gabbaı̈

2017

Organometallics

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As part of our efforts toward the discovery of new late transition metal catalysts, we synthesized [(o-(Ph 2 P)C 6 H 4 ) 2 (o-C 6 Cl 4 O 2 )SbPh)Au] + (3 + ) and [(o-(iPr 2 P)-C 6 H 4 ) 2 (o-C 6 Cl 4 O 2 )SbPh)Au] + (4 + ), two cationic bis-(phosphino)gold stiborane complexes, which were isolated as their hexafluorophosphate salts and fully characterized.Structural and computational studies indicate that the cores of these two complexes are almost structurally and electronically identical. Despite these similarities, these two complexes exhibit different catalytic activities in the hydroamination of phenylacetylene using anilines or in the cyclization of N-(prop-2-yn-1-yl)benzamide. Indeed, whereas 3 + catalyzes both reactions, we found that 4 + is inactive. The data collected on these two complexes suggest that the origin of this contrasting behavior is steric, rather than electronic, with the relatively bulky iPr 2 P ancillary ligands blocking access to the reactive gold center.

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Section: Introductionmentioning

confidence: 99%

T-Shaped Gold→Stiborane Complexes as Carbophilic Catalysts: Influence of the Peripheral Substituents

Sen

Gabbaı̈

2017

Organometallics

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“…20 Inspired by these advances and using fluoride anion affinity data as a guide, 21,22 several groups have paid a renewed attention to the properties of antimony( v ) compounds. 23–26 As part of our contribution to this area, 27–30 we were drawn by the properties of simple neutral derivatives such as triaryl-catecholato-stiboranes ( A , Fig. 1) which have been previously shown to form adducts with Lewis basic substrates.…”

Section: Introductionmentioning

confidence: 99%

Fluorinated antimony(v) derivatives: strong Lewis acidic properties and application to the complexation of formaldehyde in aqueous solutions

Tofan

Gabbaı̈

2016

Chem. Sci.

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“…The Lewis acidity of the Sb(V) compounds can be observed in arylated derivatives such as PhSbCl 4 ( 15 ) and Ph 2 SbCl 3 ( 16 ), which readily form the corresponding chloroantimonate species [PhSbCl 5 ] − ([ 15 -Cl] − ) 40 and [Ph 2 SbCl 4 ] − ([ 16 -Cl] − ) 41 when treated with an appropriate chloride salt ( Scheme 3 ). The formation of these salts may be seen as mirroring that of their +III analogues, namely, the [PhSbCl 3 ] − anion ([ 1 -Cl] − ) and [Ph 2 SbCl 2 ] − anion ([ 2 -Cl] − ) ( Scheme 2 ).…”

Section: Anion Complexation Chemistrymentioning

confidence: 99%

Binding, Sensing, And Transporting Anions with Pnictogen Bonds: The Case of Organoantimony Lewis Acids

Murphy,

Gabbaï

2023

J. Am. Chem. Soc.

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Motivated by the discovery of main group Lewis acids that could compete or possibly outperform the ubiquitous organoboranes, several groups, including ours, have engaged in the chemistry of Lewis acidic organoantimony compounds as new platforms for anion capture, sensing, and transport. Principal to this approach are the intrinsically elevated Lewis acidic properties of antimony, which greatly favor the addition of halide anions to this group 15 element. The introduction of organic substituents to the antimony center and its oxidation from the + III to the + V state provide for tunable Lewis acidity and a breadth of applications in supramolecular chemistry and catalysis. The performances of these antimony-based Lewis acids in the domain of anion sensing in aqueous media illustrate the favorable attributes of antimony as a central element. At the same time, recent advances in anion binding catalysis and anion transport across phospholipid membranes speak to the numerous opportunities that lie ahead in the chemistry of these unique main group compounds.

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Syntheses, structures and intermolecular interactions of tetraorganoammonium, -phosphonium and -stibonium dimethyl- and diphenyltetrahaloantimonates

Cited by 12 publications

References 25 publications

T-Shaped Gold→Stiborane Complexes as Carbophilic Catalysts: Influence of the Peripheral Substituents

T-Shaped Gold→Stiborane Complexes as Carbophilic Catalysts: Influence of the Peripheral Substituents

Fluorinated antimony(v) derivatives: strong Lewis acidic properties and application to the complexation of formaldehyde in aqueous solutions

Binding, Sensing, And Transporting Anions with Pnictogen Bonds: The Case of Organoantimony Lewis Acids

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