In Situ Formation of Semichelating Ligands: A Strategy for Tuning the Magnetic Coupling in Azide‐Bridged Copper(II) Complexes

Shi, Wenbo; Cui, Ai‐Li; Kou, Hui‐Zhong

doi:10.1002/cplu.201300304

Cited by 13 publications

(1 citation statement)

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“…[26][27][28][29][30][31][32][33][34][35][36][37][38][39][40][41] However, chloride-bridged octahedral-tetrahedral Cu(II) complexes have seldom been reported. [42][43][44] On the other hand, while magneto-structural correlations for azide-Cu(II) systems have been widely investigated, 45,46 those for the chloride-bridged Cu oct -Cl-Cu tet system and dicyanamide-bridged Cu 2 (μ 2 -O) 2 dinuclear systems are not well known. 43,[47][48][49][50][51][52] The coupling of Cu(II) complexes to halogen or pseudohalogen ions forms a various of complexes, and the structure can be tuned by the modification of the organic ligands.…”

Section: Introductionmentioning

confidence: 99%

Assembly of dinuclear copper(ii) secondary building units into polymeric complexes: crystal structures and magnetic properties

2014

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Four Cu(II) complexes, the one-dimensional [Cu(HL 1 ) 2 (CuCl 4 )] n (1), {[Cu 2 (L 1 ) 2 (N(CN) 2 )(CH 3 OH)](ClO 4 )} n (2), dinuclear [Cu 2 (L 2 ) 2 Cl 2 ] (3), and two-dimensional layered [Cu 2 (L 2 ) 2 (N(CN) 2 ) 2 ] n (4) were synthesized by Cu(II) salts (CuCl 2 •2H 2 O or Cu(ClO 4 ) 2 •6H 2 O), alkanol bidentate ligands trans-2-(1-pyrazolyl)cyclohexanol (HL 1 ) or3,5-dimethyl-N-hydroxyethyl-pyrazolyl (HL 2 ) together with sodium dicyanamide. For complex 1, the bridging chlorine atoms of the tetrahedral [CuCl 4 ] 2− moieties are located at the Jahn-Teller axis of the elongated octahedral Cu(II), forming an alternate elongated-octahedral-tetrahedral Cu(II) chain complex.For complexes 2, 3 and 4, the alkyl oxygen atoms of the deprotonated ligands HL 1 and HL 2 bridge two Cu(II) ions, yielding a dinuclear Cu(II) unit [Cu 2 (L x ) 2 ] 2+ (x = 1, 2), and one-or two-dimensional complexes via bridging dicyanamide ligands. Complex 1 shows weak ferromagnetic coupling, whilst complexes 2-4 display strong antiferromagnetic coupling or are even nearly diamagnetic due to the large Cu-O-Cu bond angles.

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Section: Introductionmentioning

confidence: 99%

Assembly of dinuclear copper(ii) secondary building units into polymeric complexes: crystal structures and magnetic properties

2014

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Regio‐ und chemoselektive Oxo‐Azidierung von Vinylarenen, katalysiert durch Kupfer(II) und sichtbares Licht

et al. 2018

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Die photokatalytische Oxo-Azidierung von Vinylarenen mit Trimethylsilylazid und Luftsauerstoff als stçchiometrischem Oxidationsmittel gelingt in Gegenwart von [Cu(dap) 2 ]Cl oder [Cu(dap)Cl 2 ], im Unterschied zu etablierten Photokatalysytoren auf Basis von Iridium oder Ruthenium oder organischen Farbstoffen. Eine Erklärung hierfürsind der leichte Ligandenaustauschs owie die Mçglichkeit zur Rückbindung der intermediärg ebildeten Radikale an Kupferzentren. Als katalytischa ktive Spezies wird ein Cu II -Azid-Komplex postuliert, der eine durch sichtbares Lichtb eschleunigte Cu-N-Bindungshomolyse eingeht und dabei Cu I sowie Azidradikale bildet. Dieses Aktivierungsprinzip (Cu II -X!Cu I + XC)e rçffnet neue Mçglichkeiten fürd ie Kupfer-basierte Photokatalyse.

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Visible‐Light‐Accelerated Copper(II)‐Catalyzed Regio‐ and Chemoselective Oxo‐Azidation of Vinyl Arenes

et al. 2018

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The visible-light-accelerated oxo-azidation of vinyl arenes with trimethylsilylazide and molecular oxygen as stoichiometric oxidant was achieved. In contrast to photocatalysts based on iridium, ruthenium, or organic dyes, [Cu(dap) ]Cl or [Cu(dap)Cl ] were found to be unique for this transformation, which is attributed to their ability to interact with the substrates through ligand exchange and rebound mechanisms. Cu is proposed as the catalytically active species, which upon coordinating azide will undergo light-accelerated homolysis to form Cu and azide radicals. This activation principle (Cu -X→Cu +X ) opens up new avenues for copper-based photocatalysis.

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In Situ Formation of Semichelating Ligands: A Strategy for Tuning the Magnetic Coupling in Azide‐Bridged Copper(II) Complexes

Abstract: Scheme 1. Formation processes for complexes 1-5.[a] W

Cited by 13 publications

References 65 publications

Assembly of dinuclear copper(ii) secondary building units into polymeric complexes: crystal structures and magnetic properties

Assembly of dinuclear copper(ii) secondary building units into polymeric complexes: crystal structures and magnetic properties

Regio‐ und chemoselektive Oxo‐Azidierung von Vinylarenen, katalysiert durch Kupfer(II) und sichtbares Licht

Visible‐Light‐Accelerated Copper(II)‐Catalyzed Regio‐ and Chemoselective Oxo‐Azidation of Vinyl Arenes

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