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A dynamic tetranuclear gold(I)-cyclophane -- gold (I)-centred chirality and fluxionality arising from an intramolecular shift of Au--S bonds.

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Title: A dynamic tetranuclear gold(I)-cyclophane -- gold (I)-centred chirality and fluxionality arising from an intramolecular shift of Au--S bonds.
Authors: Pau Lin Ang1, Van Ha Nguyen1,2, Yip, John H. K.1 chmyiphk@nus.edu.sg
Source: Dalton Transactions: An International Journal of Inorganic Chemistry. 9/7/2021, Vol. 50 Issue 33, p11422-11428. 7p.
Subjects: Chirality, X-ray crystallography, Nuclear magnetic resonance spectroscopy, Gold, Gold clusters, Anthracene
Abstract: A tetranuclear gold(I) complex [Au4(µ-PAnP)2(µ-L)2] (PAnP = 9,10-bis(diphenylphosphino)anthracene and L = benzene-1,2-dithiolate) has been synthesized and characterised by multinuclear NMR and X-ray crystallography. The molecule has a cyclophane-like structure which can be considered to be composed of two [Au2(µ-PAnP)(µ-L)] units held together by Au--S bonds and aurophilic interactions (Au-Au = 3.0712(2) Å). L acts as a chelating and bridging ligand with one of its S atoms bonded to two Au ions as sulfonium ions and there are two Au2S2 cores on each side of the cyclophane. A sulfur atom in each Au2S2 core is a chiral sulfonium ion, being bonded to two chemically distinct Au ions. Two Au ions are bonded to four atoms (2S, P and Au) in an asymmetric environment, making them a rare example of gold(I)-centred chirality. The two Au2S2 cores have RAu, RS and SAu, SS configurations, and the chiralities of the sulfonium ion and the gold ion are correlated. Variable-temperature NMR spectroscopy showed that the metallacyclophane undergoes rapid exchange in solution. A bond shift mechanism involving simultaneous cleavage and formation of Au-S bonds is proposed for the exchange. [ABSTRACT FROM AUTHOR]
Copyright of Dalton Transactions: An International Journal of Inorganic Chemistry is the property of Royal Society of Chemistry and its content may not be copied or emailed to multiple sites without the copyright holder's express written permission. Additionally, content may not be used with any artificial intelligence tools or machine learning technologies. However, users may print, download, or email articles for individual use. This abstract may be abridged. No warranty is given about the accuracy of the copy. Users should refer to the original published version of the material for the full abstract. (Copyright applies to all Abstracts.)
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  Data: A dynamic tetranuclear gold(I)-cyclophane -- gold (I)-centred chirality and fluxionality arising from an intramolecular shift of Au--S bonds.
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  Data: <searchLink fieldCode="AR" term="%22Pau+Lin+Ang%22">Pau Lin Ang</searchLink><relatesTo>1</relatesTo><br /><searchLink fieldCode="AR" term="%22Van+Ha+Nguyen%22">Van Ha Nguyen</searchLink><relatesTo>1,2</relatesTo><br /><searchLink fieldCode="AR" term="%22Yip%2C+John+H%2E+K%2E%22">Yip, John H. K.</searchLink><relatesTo>1</relatesTo><i> chmyiphk@nus.edu.sg</i>
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  Data: <searchLink fieldCode="JN" term="%22Dalton+Transactions%3A+An+International+Journal+of+Inorganic+Chemistry%22">Dalton Transactions: An International Journal of Inorganic Chemistry</searchLink>. 9/7/2021, Vol. 50 Issue 33, p11422-11428. 7p.
– Name: Subject
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  Data: <searchLink fieldCode="DE" term="%22Chirality%22">Chirality</searchLink><br /><searchLink fieldCode="DE" term="%22X-ray+crystallography%22">X-ray crystallography</searchLink><br /><searchLink fieldCode="DE" term="%22Nuclear+magnetic+resonance+spectroscopy%22">Nuclear magnetic resonance spectroscopy</searchLink><br /><searchLink fieldCode="DE" term="%22Gold%22">Gold</searchLink><br /><searchLink fieldCode="DE" term="%22Gold+clusters%22">Gold clusters</searchLink><br /><searchLink fieldCode="DE" term="%22Anthracene%22">Anthracene</searchLink>
– Name: Abstract
  Label: Abstract
  Group: Ab
  Data: A tetranuclear gold(I) complex [Au4(µ-PAnP)2(µ-L)2] (PAnP = 9,10-bis(diphenylphosphino)anthracene and L = benzene-1,2-dithiolate) has been synthesized and characterised by multinuclear NMR and X-ray crystallography. The molecule has a cyclophane-like structure which can be considered to be composed of two [Au2(µ-PAnP)(µ-L)] units held together by Au--S bonds and aurophilic interactions (Au-Au = 3.0712(2) Å). L acts as a chelating and bridging ligand with one of its S atoms bonded to two Au ions as sulfonium ions and there are two Au2S2 cores on each side of the cyclophane. A sulfur atom in each Au2S2 core is a chiral sulfonium ion, being bonded to two chemically distinct Au ions. Two Au ions are bonded to four atoms (2S, P and Au) in an asymmetric environment, making them a rare example of gold(I)-centred chirality. The two Au2S2 cores have RAu, RS and SAu, SS configurations, and the chiralities of the sulfonium ion and the gold ion are correlated. Variable-temperature NMR spectroscopy showed that the metallacyclophane undergoes rapid exchange in solution. A bond shift mechanism involving simultaneous cleavage and formation of Au-S bonds is proposed for the exchange. [ABSTRACT FROM AUTHOR]
– Name: AbstractSuppliedCopyright
  Label:
  Group: Ab
  Data: <i>Copyright of Dalton Transactions: An International Journal of Inorganic Chemistry is the property of Royal Society of Chemistry and its content may not be copied or emailed to multiple sites without the copyright holder's express written permission. Additionally, content may not be used with any artificial intelligence tools or machine learning technologies. However, users may print, download, or email articles for individual use. This abstract may be abridged. No warranty is given about the accuracy of the copy. Users should refer to the original published version of the material for the full abstract.</i> (Copyright applies to all Abstracts.)
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        Value: 10.1039/d1dt01984h
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        Text: English
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      – SubjectFull: Chirality
        Type: general
      – SubjectFull: X-ray crystallography
        Type: general
      – SubjectFull: Nuclear magnetic resonance spectroscopy
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      – SubjectFull: Gold
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      – SubjectFull: Gold clusters
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      – SubjectFull: Anthracene
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      – TitleFull: A dynamic tetranuclear gold(I)-cyclophane -- gold (I)-centred chirality and fluxionality arising from an intramolecular shift of Au--S bonds.
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            NameFull: Pau Lin Ang
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            – D: 07
              M: 09
              Text: 9/7/2021
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              Y: 2021
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