Transformation of 5-chloro- and 5-bromo-2-cyanopyridine to amides and iminonitriles at the Mo(IV) center

2026
journal article
article
dc.abstract.enThe reaction of $K_{3}Na[Mo(CN)_{4}O_{2}]·6H_{2}O$ complex with 5-chloro-2-cyanopyridine (5cl2py) and 5-bromo-2-cyanopyridine (5br2py), results in isolation of 4 new compounds, which were characterized by single X-ray crystal structure measurements, elemental analyses, IR and UV-Vis spectroscopy methods. Dimeric complex with the formula $(PPh_{4})_{4}[Mo(CN)_{3}O(μ-CN)Mo(CN)_{4}(H_{2}O)]·5cl2py·5H_{2}O·EtOH$ was isolated for the first time. The exchange of cyanido ligands for bidentate organic ligands, in this type of complexes, is largely pH dependent. Careful control of the reaction environment made it possible to obtain a modified organic ligand in which the nitrile group was hydrolyzed to the amide group (pH ca 8), or transformed, due to presence of cyanides in solution, to imino(5-chloropyridin-2-yl)acetonitrile (5cl2pya) or imino(5-bromopyridin-2-yl)acetonitrile (5br2pya), respectively. Two complexes with the formulas $(PPh_{4})_{2}[Mo(CN)_{3}O(5cl2pya)]·5cl2py$ and $(PPh_{4})_{2}[Mo(CN)_{3}O(5br2pya)]·5br2py$ (pH ca 10) were isolated. In these compounds, the 5cl2pya (or 5br2pya) was coordinated to the metal center as N,N-donating ligand, in which the modification of the nitrile group is discussed in detail in the paper.
dc.affiliationWydział Chemii : Zakład Chemii Nieorganicznej
dc.affiliationSzkoła Doktorska Nauk Ścisłych i Przyrodniczych
dc.contributor.authorJurowska, Anna - 163745
dc.contributor.authorKoprowska, Martyna
dc.contributor.authorBogdał, Weronika - 403452
dc.contributor.authorHodorowicz, Maciej - 128328
dc.contributor.authorSzklarzewicz, Janusz - 132237
dc.date.accession2025-10-10
dc.date.accessioned2025-10-10T14:07:17Z
dc.date.available2025-10-10T14:07:17Z
dc.date.createdat2025-10-08T08:39:29Zen
dc.date.issued2026
dc.date.openaccess0
dc.description.accesstimew momencie opublikowania
dc.description.versionostateczna wersja wydawcy
dc.description.volume1350
dc.identifier.articleid143979
dc.identifier.doi10.1016/j.molstruc.2025.143979
dc.identifier.issn0022-2860
dc.identifier.projectDRC AI
dc.identifier.urihttps://ruj.uj.edu.pl/handle/item/562497
dc.identifier.weblinkhttps://www.sciencedirect.com/science/article/pii/S0022286025026250?via%3Dihub
dc.languageeng
dc.language.containereng
dc.rightsUdzielam licencji. Uznanie autorstwa 4.0 Międzynarodowa
dc.rights.licenceCC-BY
dc.rights.urihttp://creativecommons.org/licenses/by/4.0/legalcode.pl
dc.share.typeinne
dc.source.integratorfalse
dc.subject.enmolybdenum
dc.subject.ennitriles
dc.subject.encyanides
dc.subject.enstructure
dc.subject.enligand modification
dc.subtypeArticle
dc.titleTransformation of 5-chloro- and 5-bromo-2-cyanopyridine to amides and iminonitriles at the Mo(IV) center
dc.title.journalJournal of Molecular Structure
dc.typeJournalArticle
dspace.entity.typePublicationen
dc.abstract.en
The reaction of $K_{3}Na[Mo(CN)_{4}O_{2}]·6H_{2}O$ complex with 5-chloro-2-cyanopyridine (5cl2py) and 5-bromo-2-cyanopyridine (5br2py), results in isolation of 4 new compounds, which were characterized by single X-ray crystal structure measurements, elemental analyses, IR and UV-Vis spectroscopy methods. Dimeric complex with the formula $(PPh_{4})_{4}[Mo(CN)_{3}O(μ-CN)Mo(CN)_{4}(H_{2}O)]·5cl2py·5H_{2}O·EtOH$ was isolated for the first time. The exchange of cyanido ligands for bidentate organic ligands, in this type of complexes, is largely pH dependent. Careful control of the reaction environment made it possible to obtain a modified organic ligand in which the nitrile group was hydrolyzed to the amide group (pH ca 8), or transformed, due to presence of cyanides in solution, to imino(5-chloropyridin-2-yl)acetonitrile (5cl2pya) or imino(5-bromopyridin-2-yl)acetonitrile (5br2pya), respectively. Two complexes with the formulas $(PPh_{4})_{2}[Mo(CN)_{3}O(5cl2pya)]·5cl2py$ and $(PPh_{4})_{2}[Mo(CN)_{3}O(5br2pya)]·5br2py$ (pH ca 10) were isolated. In these compounds, the 5cl2pya (or 5br2pya) was coordinated to the metal center as N,N-donating ligand, in which the modification of the nitrile group is discussed in detail in the paper.
dc.affiliation
Wydział Chemii : Zakład Chemii Nieorganicznej
dc.affiliation
Szkoła Doktorska Nauk Ścisłych i Przyrodniczych
dc.contributor.author
Jurowska, Anna - 163745
dc.contributor.author
Koprowska, Martyna
dc.contributor.author
Bogdał, Weronika - 403452
dc.contributor.author
Hodorowicz, Maciej - 128328
dc.contributor.author
Szklarzewicz, Janusz - 132237
dc.date.accession
2025-10-10
dc.date.accessioned
2025-10-10T14:07:17Z
dc.date.available
2025-10-10T14:07:17Z
dc.date.createdaten
2025-10-08T08:39:29Z
dc.date.issued
2026
dc.date.openaccess
0
dc.description.accesstime
w momencie opublikowania
dc.description.version
ostateczna wersja wydawcy
dc.description.volume
1350
dc.identifier.articleid
143979
dc.identifier.doi
10.1016/j.molstruc.2025.143979
dc.identifier.issn
0022-2860
dc.identifier.project
DRC AI
dc.identifier.uri
https://ruj.uj.edu.pl/handle/item/562497
dc.identifier.weblink
https://www.sciencedirect.com/science/article/pii/S0022286025026250?via%3Dihub
dc.language
eng
dc.language.container
eng
dc.rights
Udzielam licencji. Uznanie autorstwa 4.0 Międzynarodowa
dc.rights.licence
CC-BY
dc.rights.uri
http://creativecommons.org/licenses/by/4.0/legalcode.pl
dc.share.type
inne
dc.source.integrator
false
dc.subject.en
molybdenum
dc.subject.en
nitriles
dc.subject.en
cyanides
dc.subject.en
structure
dc.subject.en
ligand modification
dc.subtype
Article
dc.title
Transformation of 5-chloro- and 5-bromo-2-cyanopyridine to amides and iminonitriles at the Mo(IV) center
dc.title.journal
Journal of Molecular Structure
dc.type
JournalArticle
dspace.entity.typeen
Publication
Affiliations

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