Crystal structure and magnetic properties of a μ-halogeno-bridged copper(II) chain with neutral planar [Cu(batt)Cl] units (Hbatt = 1,3-bis[3-(5-amino-1,2,4-triazolyl)]triazene)

Hanot, V.; Robert, T.; Kolnaar, Jeroen J. A.; Haasnoot, Jaap G.; Kooijman, Huub; Spek, Anthony L.

doi:10.1016/s0020-1693(96)05443-6

Cited by 12 publications

(5 citation statements)

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“…Polymeric Cu(1,3-bis[3-(5-amino-1,2,4-triazolyl)]triazene)chloride crystallizes with a triazene linking two amino-substituted triazole units . This planar molecule serves as a tridentate ligand to one copper(II) atom, and this along with bonding to the chloride atom [2.268(2) Å] establishes an equatorial plane.…”

Section: Discussionmentioning

confidence: 99%

“…Polymeric Cu(1,3-bis[3-(5-amino-1,2,4-triazolyl)]triazene)chloride crystallizes with a triazene linking two aminosubstituted triazole units. 38 This planar molecule serves as a tridentate ligand to one copper(II) atom, and this along with bonding to the chloride atom [2.268(2) Å] establishes an equatorial plane. The copper is further bonded to the chloride atom of a neighboring copper atom {[Cu-Cl ) 2.586(2) Å], [Cu-Cu ) 3.5874(2) Å], [Cu-Cl-Cu ) 95.06(7) Å]}.…”

Section: Discussionmentioning

confidence: 99%

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Intermolecular Magnetic Couplings in the Dinuclear Copper(II) Complex μ-Chloro-μ-[2,5-bis(2-pyridyl)-1,3,4-thiadiazole] Aqua Chlorocopper(II) Dichlorocopper(II): Synthesis, Crystal Structure, and EPR and Magnetic Characterization

et al. 2004

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Mu-chloro-mu-[2,5-bis(2-pyridyl)-1,3,4-thiadiazole] aqua chlorocopper(II) dichlorocopper(II) is the first characterized dimeric complex of a transition metal and this hetero ligand [C(12)H(10)Cl(4)Cu(2)N(4)OS; triclinic; space group P; a = 9.296(3) A, b = 9.933(3) A, c = 10.412(3) A; alpha = 79.054(5) degrees, beta = 82.478(6) degrees, gamma = 67.099(5) degrees; Z = 2 at room temperature]. The Cu(II) ions are bridged by the N-N thiadiazole bond and a chloride ion [Cu1-Cu2 = 3.7800(8) A]. Thermogravimetric analysis shows this structure to be stable at temperatures up to 348 K. At higher temperatures, the successive loss of a water molecule and one chloride of the dimeric unit is identified. From room temperature to 125 K, half of the Cu(2+) ions are progressively engaged in intermolecular dinuclear antiferromagnetic exchanges, while the other half remain paramagnetic. At lower temperatures, both susceptibility and electron paramagnetic resonance measurements show the paramagnetic-only couplings of this half of the Cu(2+) ions, involving a singlet ground state for interacting Cu(2+). This unusual behavior has been satisfactorily explained on the basis of intermolecular Cu-Cu interactions (J = -180 cm(-1)), involving the magnetic d(z)2 orbital perpendicular to the molecular plane, on which are seen the conjugate effects of the bridging chloride and the planar thiadiazole. It is noteworthy that the behavior of the title compound is original, compared to the systematic in-plane intramolecular antiferromagnetic coupling of other thiadiazole-containing binuclear complexes.

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Section: Discussionmentioning

confidence: 99%

Section: Discussionmentioning

confidence: 99%

Intermolecular Magnetic Couplings in the Dinuclear Copper(II) Complex μ-Chloro-μ-[2,5-bis(2-pyridyl)-1,3,4-thiadiazole] Aqua Chlorocopper(II) Dichlorocopper(II): Synthesis, Crystal Structure, and EPR and Magnetic Characterization

et al. 2004

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“…1 H NMR (DMSO-d 6 , 300 MHz, δ): 4.08 (s, 12H), 7.98 (s, 4H) ppm. 13 4-(Dimethylamino)-1-methyltriazolium hexafluoridophosphate (0.31 g, 0.0011 mol) and 2-azido-1,3-dimethoxyimidazolium hexafluoridophosphate (0.36 g, 0.0011 mol) were dissolved in CH 3 CN (5 mL). The resulting solution was cooled to 0˝C, and NaH (0.05 g, 0.0011 mol) was slowly added.…”

Section: Methodsmentioning

confidence: 99%

2-Azidoimidazolium Ions Captured by N-Heterocyclic Carbenes: Azole-Substituted Triazatrimethine Cyanines

et al. 2016

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1,3-Disubstituted 2-azidoimidazolium salts (substituents = methyl, methoxy; anion = PF 6 ) reacted with N-heterocyclic carbenes to yield yellow 2-(1-(azolinylidene)triazen-3-yl)-1,3-R 2 -imidazolium salts (azole = 1,3-dimethylimidazole, 1,3-dimethoxyimidazole, 4-dimethylamino-1-methyl-1,2,4-triazole; R = methyl, methoxy; anion = PF 6 ). Crystal structures of three cationic triazenes were determined. Numerous interionic C-H¨¨¨F contacts were observed. Solvatochromism of the triazenes in polar solvents was investigated by UV-Vis spectroscopy, involving the dipolarity π* and hydrogen-bond donor acidity α of the solvent. Cyclovoltammetry showed irreversible reduction of the cations to uncharged radicals. Thermoanalysis showed exothermal decomposition.

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“…Perhaps more importantly, triazenide ligands may form coordination complexes involving the internal nitrogen lone-pair. Despite this clear potential, structurally characterized instances are scant and are restricted to derivatives of tetrazole-substituted triazines in which additional metal to ligand interactions provide a template to favor coordination at the internal nitrogen …”

Section: Introductionmentioning

confidence: 99%

Triazenide Complexes of the Heavier Alkaline Earths: Synthesis, Characterization, And Suitability for Hydroamination Catalysis

et al. 2008

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A series of triazenide complexes of the heavier alkaline earths, Ca, Sr and Ba, have been synthesized by either protonolysis or salt metathesis routes. Although complexes of the form [{Ar 2N 3}M{N(SiMe 3) 2}(THF) n ] (M = Ca, n = 2; M = Sr, n = 3; Ar = 2,6-diisopropylphenyl) and [{Ar 2N 3}Ca(I)(THF) 2] 2 could be isolated and characterized by X-ray crystallography, solution studies revealed the propensity of these species to undergo Schlenk-like redistribution with the formation of [{Ar 2N 3} 2M(THF) n ] (M = Ca, n = 1; M = Sr, n = 2). The latter compounds have been synthesized independently. In the case of the large barium dication, attempts to synthesize the heaviest analogue of the series, [{Ar 2N 3} 2Ba(THF) n ], failed and led instead to the isolation of the potassium barate complex [K{Ar 2N 3}Ba{N(SiMe 3) 2} 2(THF) 4]. Single crystal X-ray diffraction studies demonstrated that, although in all the aforementioned cases the triazenide ligand binds to the electrophilic group 2 metal centers via symmetrical kappa (2)- N, N-chelates, in the latter compound an unprecedented bridging mode is observed in which the triazenide ligand coordinates through both terminal and internal nitrogen centers. A series of density-functional theory computational experiments have been undertaken to assist in our understanding of this phenomenon. In further experiments, the calcium and strontium amide derivatives [{Ar 2N 3}M{N(SiMe 3) 2}(THF) n ] (M = Ca, n = 2; M = Sr, n = 3) proved to be catalytically active for the intramolecular hydroamination of 1-amino-2,2-diphenylpent-4-ene to form 2-methyl-4,4-diphenylpyrrolidine, with the calcium species demonstrating a higher turnover number than the strontium analogue ( 2a, TOF = 500 h (-1); 2b, TOF = 75 h (-1)). In these instances, because of ambiguities in the structural charcterization of the precatalyst in solution, such quantification holds little value and detailed catalytic studies have not been conducted.

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Crystal structure and magnetic properties of a μ-halogeno-bridged copper(II) chain with neutral planar [Cu(batt)Cl] units (Hbatt = 1,3-bis[3-(5-amino-1,2,4-triazolyl)]triazene)

Cited by 12 publications

References 10 publications

Intermolecular Magnetic Couplings in the Dinuclear Copper(II) Complex μ-Chloro-μ-[2,5-bis(2-pyridyl)-1,3,4-thiadiazole] Aqua Chlorocopper(II) Dichlorocopper(II): Synthesis, Crystal Structure, and EPR and Magnetic Characterization

Intermolecular Magnetic Couplings in the Dinuclear Copper(II) Complex μ-Chloro-μ-[2,5-bis(2-pyridyl)-1,3,4-thiadiazole] Aqua Chlorocopper(II) Dichlorocopper(II): Synthesis, Crystal Structure, and EPR and Magnetic Characterization

2-Azidoimidazolium Ions Captured by N-Heterocyclic Carbenes: Azole-Substituted Triazatrimethine Cyanines

Triazenide Complexes of the Heavier Alkaline Earths: Synthesis, Characterization, And Suitability for Hydroamination Catalysis

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