Stannylen oder Metallastanna(IV)‐ocan – eine Sache des Formalismus

Brendler, Erica; Wächtler, Eberhard; Heine, Thomas; Zhechkov, Lyuben; Langer, Thor﻿s﻿ten; Pöttgen, Rainer; Hill, Anthony F.; Wagler, Jörg

doi:10.1002/ange.201007967

Cited by 16 publications

(9 citation statements)

References 57 publications

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“…In this respect, the synthesis of 2 stands out because it is achieved by oxidation of a pre-assembled complex. [17] To conclude this study, it became important for us to address the reversibility of the redox process supported by this new dinuclear platform. Having already shown that 1 can be cleanly oxidized into 2, we decided to test the reverse reaction.…”

Section: Methodsmentioning

confidence: 99%

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

Wade¹,

Gabbaı̈²

2011

Angewandte Chemie

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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 prima...

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Section: Methodsmentioning

confidence: 99%

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

Wade¹,

Gabbaı̈²

2011

Angewandte Chemie

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“…Elemental analyses were carried out on aC /H/N/S analyser "Vario Micro Cube" (Elementar). [36] The NBO calculations of the Sb reference compounds were based on the X-ray structures reported for:[ (MeCÀNiPr) 2 CÀSCN] + [SbF 6 ] À , [37] OSbPh 3 , [22b] [SbPh 4 ] + [I 3 ] À , [38] [Me-CO] + [SbCl 6 ] À , [39] [PPh 4 ] + [SbBr 6 ] À , [40] [NEt 4 ] + [Sb(C 6 H 4 S 2 ) 3 ] À , [41] (bipy)SbF 3 , [42] (bipy)SbCl 3 , [43] [SbCl 5 ] 2À , [44] [HNC 5 H 4 ] + [SbCl 4 ] À , [45] SbPh 3 [46] (if applicable, positions of Ha toms were optimized prior to NBO analysis). The samples were enclosed in PMMA containers.…”

Section: Materials and Equipmentmentioning

confidence: 99%

“…Unlike the TM10-Si (TM10:G roup 10 metal) paddlewheel compounds featuring methimazolyl Scheme2.Au/Tec omplex IV in its reduced and oxidized form and the scope of this work,i ncomparison. (2), Sb1ÀN1 2.479(2), Sb1ÀN2 2.684(2), Sb1ÀN3 2.297(2), Sb1ÀN4 2.266(2), Rh1ÀS1 2.3452(6), Rh1ÀS2 2.3788(6), Rh1ÀS3 2.3700(6), Rh1ÀS4 2.3359(6), Rh1ÀS2* 2.5322(5); 2:S b1ÀRh1 2.4880(6), Sb1ÀO1 1.944(4), Sb1À O1* 2.062(4), Sb1ÀN1 2.274(5), Sb1ÀN2 2.276(4), Sb1ÀN3 2.299(4), Rh1ÀS1 2.333(2), Rh1ÀS2 2.303(2),R h1ÀS3 2.228(2), Rh1ÀS4 2.425(2), Rh1ÀN4 2.094 (5).…”

Section: Synthesesmentioning

confidence: 99%

“…For example, in an eutral complex [MÀM'(m-X) 4 ]w ith ah eterometallic core and four monoanionic bridging ligands, both metal atoms Ma nd M'a re automatically assigned the formal oxidation numbers (+ II). [4] For heterobimetallic Pd/Sn systems featuring mt [5] or pyS [6] ligands, the charged elocalization within the bridging ligands leads to more ambiguous assignment of bondings ituations between the metal atoms, that is, it raises the question of whether the Group 14 elements (E 14 ) should be referred to as s-acceptor (TM!E 14 , III Z )o rs-donor (TM ! Thus, elucidation of the electronic features of intermetallicb onds is of great interest.…”

Section: Introductionmentioning

confidence: 98%

“…Recently, for paddlewheel-shaped Ni, Pd, and Pt complexes, we have shown that the mt ligand can also be utilized for the stabilization of dative interactions between TMs and electronically saturated Si and Sn compounds (TM!Si/Sn, Group 14 Zligands, for example, II). [4] For heterobimetallic Pd/Sn systems featuring mt [5] or pyS [6] ligands, the charged elocalization within the bridging ligands leads to more ambiguous assignment of bondings ituations between the metal atoms, that is, it raises the question of whether the Group 14 elements (E 14 ) should be referred to as s-acceptor (TM!E 14 , III Z )o rs-donor (TM ! E 14 , III L ), or the intermediate case with ac ovalent metalmetal bond (TMÀE 14 , III X ,S cheme 1; this feature was also reportedf or related complexes bearing 2-pyridyldiphenylphosphine [7] or ortho-metallated arsines [8] as bridgingligands).…”

Section: Introductionmentioning

confidence: 99%

See 2 more Smart Citations

Synthesis and Oxidation of a Paddlewheel‐Shaped Rhodium/Antimony Complex Featuring Pyridine‐2‐Thiolate Ligands

Wächtler

Oro

Iglesias

et al. 2017

Chemistry A European J

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The paddlewheel-shaped complex [Sb(μ-pyS) Rh] (1) (pyS = 2-S-C H N ) was synthesized from [Rh(pyS)(cod)] (cod=1,5-cyclooctadiene) and Sb(pyS) . Upon oxidation with ONMe , the complex [(μ-O)Sb(μ-pyS) Rh(κ -pyS)] (2) is formed. Both 1 and 2 form dimers and feature short Rh-Sb bonds and bridging pyS ligands. Sb Mössbauer spectro- scopy and computational studies were employed to elucidate the Rh-Sb bonding in 1 and 2. Both covalent (Rh-Sb, X-type Sb ligand) and dative (Rh→Sb, Z-type; Rh←Sb L-type Sb ligand) interactions have to be considered for the description of their bonding situations.

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Telluronium Ions as σ‐Acceptor Ligands

Lin

Gabbaı̈

2013

Angewandte Chemie

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Stannylen oder Metallastanna(IV)‐ocan – eine Sache des Formalismus

Cited by 16 publications

References 57 publications

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

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

Synthesis and Oxidation of a Paddlewheel‐Shaped Rhodium/Antimony Complex Featuring Pyridine‐2‐Thiolate Ligands

Telluronium Ions as σ‐Acceptor Ligands

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