Synthesis and characterization of azidobipyridyl ruthenium complexes and their "click" chemistry derivatives

Baljinder S. Uppal, Adam Zahid, Paul I.P. Elliott

Research output: Contribution to journalArticle

17 Citations (Scopus)

Abstract

The ligand 4-azido-2,2′-bipyridyl (1) has been used to prepare 1,2,3-triazole-substituted ligands through copper-catalyzed alkyne/azide cycloaddition (CuAAC or "click" chemistry) with phenylacetylene, ethynylferrocene and 2-ethynylpyridine to yield 4-(4-phenyl-1,2,3-triazol-1-yl)- 2,2′-bipyridyl (2a), 4-(4-ferrocenyl-1,2,3-triazol-1-yl)-2,2′- bipyridyl (2b) and 4-[4-(pyridyl-2-yl)-1,2,3-triazol-1-yl]-2,2′-bipyridyl (2c). Complexes of the form [Ru(p-cymene)(Cl)(L)]PF6 (3, L = 1; 4a, L = 2a; 4b, L = 2b) were then prepared and characterized. We also report the synthesis of the complex of the analogous ligand 4,4′-bisazido-2,2′- bipyridyl (1′), [Ru(p-cymene)(Cl)(1′)]PF6 (3′). Complexes 4a and 4b were also prepared by an alternative route, whereby 3 undergoes CuAAC coupling with phenylacetylene and ethynylferrocene respectively. Complexes prepared with ligands that are pre-assembled or "clicked" at the metal show identical 1H NMR spectra. CuAAC coupling of 3 and 2-ethynylpyridine results in the formation of the complex [Ru(p-cymene)(Cl)(2c)] PF6 (4c), which contains a coordinatively vacant pyridyltriazole moiety. The reaction of [Ru(p-cymene)(Cl)2]2 with pre-assembled 2c results in the formation of the dinuclear complex [{Ru(p-cymene)(Cl)}2(2c)]·2PF6 (5), which incorporates ruthenium atoms at both bipyridyl and pyridyltriazole binding domains. The 1H NMR spectrum of the complex shows two signals for the triazole ring proton as well as duplicate signals for other protons of the bridging ligand, which indicates that 5 is produced as a mixture of diastereoisomers. The complex [{Ru(p-cymene)Cl}2{di-4-([1-{2, 2′-bipyrid-4-yl}triazol-4-yl]methyl)ether}][PF6]2 (7) was also prepared through the coupling of 3 with dipropargyl ether.

LanguageEnglish
Pages2571-2579
Number of pages9
JournalEuropean Journal of Inorganic Chemistry
Volume2013
Issue number14
DOIs
Publication statusPublished - 1 May 2013

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2,2'-Dipyridyl
Ruthenium
Derivatives
Ligands
Triazoles
Protons
Nuclear magnetic resonance
Methyl Ethers
Alkynes
Azides
Cycloaddition
Ether
4-cymene
Copper
Metals
Atoms

Cite this

@article{9f7fd43d929348d9b12b13dbc5c9394c,
title = "Synthesis and characterization of azidobipyridyl ruthenium complexes and their {"}click{"} chemistry derivatives",
abstract = "The ligand 4-azido-2,2′-bipyridyl (1) has been used to prepare 1,2,3-triazole-substituted ligands through copper-catalyzed alkyne/azide cycloaddition (CuAAC or {"}click{"} chemistry) with phenylacetylene, ethynylferrocene and 2-ethynylpyridine to yield 4-(4-phenyl-1,2,3-triazol-1-yl)- 2,2′-bipyridyl (2a), 4-(4-ferrocenyl-1,2,3-triazol-1-yl)-2,2′- bipyridyl (2b) and 4-[4-(pyridyl-2-yl)-1,2,3-triazol-1-yl]-2,2′-bipyridyl (2c). Complexes of the form [Ru(p-cymene)(Cl)(L)]PF6 (3, L = 1; 4a, L = 2a; 4b, L = 2b) were then prepared and characterized. We also report the synthesis of the complex of the analogous ligand 4,4′-bisazido-2,2′- bipyridyl (1′), [Ru(p-cymene)(Cl)(1′)]PF6 (3′). Complexes 4a and 4b were also prepared by an alternative route, whereby 3 undergoes CuAAC coupling with phenylacetylene and ethynylferrocene respectively. Complexes prepared with ligands that are pre-assembled or {"}clicked{"} at the metal show identical 1H NMR spectra. CuAAC coupling of 3 and 2-ethynylpyridine results in the formation of the complex [Ru(p-cymene)(Cl)(2c)] PF6 (4c), which contains a coordinatively vacant pyridyltriazole moiety. The reaction of [Ru(p-cymene)(Cl)2]2 with pre-assembled 2c results in the formation of the dinuclear complex [{Ru(p-cymene)(Cl)}2(2c)]·2PF6 (5), which incorporates ruthenium atoms at both bipyridyl and pyridyltriazole binding domains. The 1H NMR spectrum of the complex shows two signals for the triazole ring proton as well as duplicate signals for other protons of the bridging ligand, which indicates that 5 is produced as a mixture of diastereoisomers. The complex [{Ru(p-cymene)Cl}2{di-4-([1-{2, 2′-bipyrid-4-yl}triazol-4-yl]methyl)ether}][PF6]2 (7) was also prepared through the coupling of 3 with dipropargyl ether.",
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author = "Uppal, {Baljinder S.} and Adam Zahid and Elliott, {Paul I.P.}",
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Synthesis and characterization of azidobipyridyl ruthenium complexes and their "click" chemistry derivatives. / Uppal, Baljinder S.; Zahid, Adam; Elliott, Paul I.P.

In: European Journal of Inorganic Chemistry, Vol. 2013, No. 14, 01.05.2013, p. 2571-2579.

Research output: Contribution to journalArticle

TY - JOUR

T1 - Synthesis and characterization of azidobipyridyl ruthenium complexes and their "click" chemistry derivatives

AU - Uppal, Baljinder S.

AU - Zahid, Adam

AU - Elliott, Paul I.P.

PY - 2013/5/1

Y1 - 2013/5/1

N2 - The ligand 4-azido-2,2′-bipyridyl (1) has been used to prepare 1,2,3-triazole-substituted ligands through copper-catalyzed alkyne/azide cycloaddition (CuAAC or "click" chemistry) with phenylacetylene, ethynylferrocene and 2-ethynylpyridine to yield 4-(4-phenyl-1,2,3-triazol-1-yl)- 2,2′-bipyridyl (2a), 4-(4-ferrocenyl-1,2,3-triazol-1-yl)-2,2′- bipyridyl (2b) and 4-[4-(pyridyl-2-yl)-1,2,3-triazol-1-yl]-2,2′-bipyridyl (2c). Complexes of the form [Ru(p-cymene)(Cl)(L)]PF6 (3, L = 1; 4a, L = 2a; 4b, L = 2b) were then prepared and characterized. We also report the synthesis of the complex of the analogous ligand 4,4′-bisazido-2,2′- bipyridyl (1′), [Ru(p-cymene)(Cl)(1′)]PF6 (3′). Complexes 4a and 4b were also prepared by an alternative route, whereby 3 undergoes CuAAC coupling with phenylacetylene and ethynylferrocene respectively. Complexes prepared with ligands that are pre-assembled or "clicked" at the metal show identical 1H NMR spectra. CuAAC coupling of 3 and 2-ethynylpyridine results in the formation of the complex [Ru(p-cymene)(Cl)(2c)] PF6 (4c), which contains a coordinatively vacant pyridyltriazole moiety. The reaction of [Ru(p-cymene)(Cl)2]2 with pre-assembled 2c results in the formation of the dinuclear complex [{Ru(p-cymene)(Cl)}2(2c)]·2PF6 (5), which incorporates ruthenium atoms at both bipyridyl and pyridyltriazole binding domains. The 1H NMR spectrum of the complex shows two signals for the triazole ring proton as well as duplicate signals for other protons of the bridging ligand, which indicates that 5 is produced as a mixture of diastereoisomers. The complex [{Ru(p-cymene)Cl}2{di-4-([1-{2, 2′-bipyrid-4-yl}triazol-4-yl]methyl)ether}][PF6]2 (7) was also prepared through the coupling of 3 with dipropargyl ether.

AB - The ligand 4-azido-2,2′-bipyridyl (1) has been used to prepare 1,2,3-triazole-substituted ligands through copper-catalyzed alkyne/azide cycloaddition (CuAAC or "click" chemistry) with phenylacetylene, ethynylferrocene and 2-ethynylpyridine to yield 4-(4-phenyl-1,2,3-triazol-1-yl)- 2,2′-bipyridyl (2a), 4-(4-ferrocenyl-1,2,3-triazol-1-yl)-2,2′- bipyridyl (2b) and 4-[4-(pyridyl-2-yl)-1,2,3-triazol-1-yl]-2,2′-bipyridyl (2c). Complexes of the form [Ru(p-cymene)(Cl)(L)]PF6 (3, L = 1; 4a, L = 2a; 4b, L = 2b) were then prepared and characterized. We also report the synthesis of the complex of the analogous ligand 4,4′-bisazido-2,2′- bipyridyl (1′), [Ru(p-cymene)(Cl)(1′)]PF6 (3′). Complexes 4a and 4b were also prepared by an alternative route, whereby 3 undergoes CuAAC coupling with phenylacetylene and ethynylferrocene respectively. Complexes prepared with ligands that are pre-assembled or "clicked" at the metal show identical 1H NMR spectra. CuAAC coupling of 3 and 2-ethynylpyridine results in the formation of the complex [Ru(p-cymene)(Cl)(2c)] PF6 (4c), which contains a coordinatively vacant pyridyltriazole moiety. The reaction of [Ru(p-cymene)(Cl)2]2 with pre-assembled 2c results in the formation of the dinuclear complex [{Ru(p-cymene)(Cl)}2(2c)]·2PF6 (5), which incorporates ruthenium atoms at both bipyridyl and pyridyltriazole binding domains. The 1H NMR spectrum of the complex shows two signals for the triazole ring proton as well as duplicate signals for other protons of the bridging ligand, which indicates that 5 is produced as a mixture of diastereoisomers. The complex [{Ru(p-cymene)Cl}2{di-4-([1-{2, 2′-bipyrid-4-yl}triazol-4-yl]methyl)ether}][PF6]2 (7) was also prepared through the coupling of 3 with dipropargyl ether.

KW - Click chemistry

KW - N ligands

KW - Ruthenium

KW - Supramolecular chemistry

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U2 - 10.1002/ejic.201201419

DO - 10.1002/ejic.201201419

M3 - Article

VL - 2013

SP - 2571

EP - 2579

JO - VDI-Berichte

T2 - VDI-Berichte

JF - VDI-Berichte

SN - 1434-1948

IS - 14

ER -