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Impact of halogen-bonding interactions on M–X bond activation pathways: a perspective.

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Title: Impact of halogen-bonding interactions on M–X bond activation pathways: a perspective.
Authors: Maiti, Sritama1 (AUTHOR) icsgxav@gmail.com, Maitra, Sreeja1 (AUTHOR), Kanrar, Gopal1 (AUTHOR), Sarkar, Koushik1 (AUTHOR), Pramanik, Kausikisankar2 (AUTHOR), Ganguly, Sanjib1 (AUTHOR)
Source: CrystEngComm. 3/2/2026, Vol. 28 Issue 9, p1470-1484. 15p.
Subjects: Metal halides, Ligand exchange reactions, Reaction mechanisms (Chemistry), Organocatalysis, Supramolecular chemistry, Chemical bonds
Abstract: The halogen bond (XB) is denoted as R–X⋯Y, where the halogen atom X is covalently linked to the R group and possesses a potentially electrophilic region on its electrostatic potential surface, while Y is an anionic/neutral species with at least one nucleophilic centre that may donate electron density (an XB acceptor). For more than two decades, scientists have worked to clarify the nature of halogen bonds in order to advance their applications. Halogen bond finds utility in the absorption of drugs and their delivery to the target tissues, and thyroid hormones T3 and T4 serve as XB donors in biomolecular systems. This concept has also been explored in organocatalysis, supramolecular chemistry as well as in crystal engineering. There are only a few reports of metal-mediated transformation via XB. In fact, there are only few cases of XB formation to metal halides where some other ligands behave as Lewis bases in the complexes. Ligand exchange via the formation of a halogen bond (XB) has been observed only in a few cases, but this finding is very useful for the development of M–X bond activation processes that are stimulated by halogen-bond formation in certain intermediate steps. In this perspective article, we summarize the key developments in this field, where the role of XB in metal-halogen bond activation with concomitant substitution is discussed with some details on the theoretical mechanistic insights and relevant experimental evidences. [ABSTRACT FROM AUTHOR]
Copyright of CrystEngComm 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.)
Database: Engineering Source
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Header DbId: egs
DbLabel: Engineering Source
An: 191987814
AccessLevel: 6
PubType: Academic Journal
PubTypeId: academicJournal
PreciseRelevancyScore: 0
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  Data: Impact of halogen-bonding interactions on M–X bond activation pathways: a perspective.
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  Data: <searchLink fieldCode="AR" term="%22Maiti%2C+Sritama%22">Maiti, Sritama</searchLink><relatesTo>1</relatesTo> (AUTHOR)<i> icsgxav@gmail.com</i><br /><searchLink fieldCode="AR" term="%22Maitra%2C+Sreeja%22">Maitra, Sreeja</searchLink><relatesTo>1</relatesTo> (AUTHOR)<br /><searchLink fieldCode="AR" term="%22Kanrar%2C+Gopal%22">Kanrar, Gopal</searchLink><relatesTo>1</relatesTo> (AUTHOR)<br /><searchLink fieldCode="AR" term="%22Sarkar%2C+Koushik%22">Sarkar, Koushik</searchLink><relatesTo>1</relatesTo> (AUTHOR)<br /><searchLink fieldCode="AR" term="%22Pramanik%2C+Kausikisankar%22">Pramanik, Kausikisankar</searchLink><relatesTo>2</relatesTo> (AUTHOR)<br /><searchLink fieldCode="AR" term="%22Ganguly%2C+Sanjib%22">Ganguly, Sanjib</searchLink><relatesTo>1</relatesTo> (AUTHOR)
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  Data: <searchLink fieldCode="JN" term="%22CrystEngComm%22">CrystEngComm</searchLink>. 3/2/2026, Vol. 28 Issue 9, p1470-1484. 15p.
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  Data: <searchLink fieldCode="DE" term="%22Metal+halides%22">Metal halides</searchLink><br /><searchLink fieldCode="DE" term="%22Ligand+exchange+reactions%22">Ligand exchange reactions</searchLink><br /><searchLink fieldCode="DE" term="%22Reaction+mechanisms+%28Chemistry%29%22">Reaction mechanisms (Chemistry)</searchLink><br /><searchLink fieldCode="DE" term="%22Organocatalysis%22">Organocatalysis</searchLink><br /><searchLink fieldCode="DE" term="%22Supramolecular+chemistry%22">Supramolecular chemistry</searchLink><br /><searchLink fieldCode="DE" term="%22Chemical+bonds%22">Chemical bonds</searchLink>
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  Data: The halogen bond (XB) is denoted as R–X⋯Y, where the halogen atom X is covalently linked to the R group and possesses a potentially electrophilic region on its electrostatic potential surface, while Y is an anionic/neutral species with at least one nucleophilic centre that may donate electron density (an XB acceptor). For more than two decades, scientists have worked to clarify the nature of halogen bonds in order to advance their applications. Halogen bond finds utility in the absorption of drugs and their delivery to the target tissues, and thyroid hormones T3 and T4 serve as XB donors in biomolecular systems. This concept has also been explored in organocatalysis, supramolecular chemistry as well as in crystal engineering. There are only a few reports of metal-mediated transformation via XB. In fact, there are only few cases of XB formation to metal halides where some other ligands behave as Lewis bases in the complexes. Ligand exchange via the formation of a halogen bond (XB) has been observed only in a few cases, but this finding is very useful for the development of M–X bond activation processes that are stimulated by halogen-bond formation in certain intermediate steps. In this perspective article, we summarize the key developments in this field, where the role of XB in metal-halogen bond activation with concomitant substitution is discussed with some details on the theoretical mechanistic insights and relevant experimental evidences. [ABSTRACT FROM AUTHOR]
– Name: AbstractSuppliedCopyright
  Label:
  Group: Ab
  Data: <i>Copyright of CrystEngComm 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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      – TitleFull: Impact of halogen-bonding interactions on M–X bond activation pathways: a perspective.
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              Text: 3/2/2026
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