DFT and Experimental Studies of Perchlorate Ion Coordination incis/trans‐Copper(II) Complexes of Tetradentate Pyridyl Ligands

Thangarasu, Pandiyan; Guadalupe, Hernández J.; Cruz, Javier; Bernès, Syl­vain; Ugalde‐Salvdivar, Víctor M.; González, Ignacio

doi:10.1002/ejic.200800091

Cited by 19 publications

(15 citation statements)

References 61 publications

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“…The redox behaviors of [Cu(LMe2)] 2+ have also been reported. 2,3 The crystal structures of chromium(III) 4 and manganese(II) 5 with LMe2 and [Cu(ClO4)2(LMe2)] 6 have been reported. A couple of perchlorate ions in the [Cu(ClO4)2(LMe2)] coordinate to the [Cu(LMe2)] 2+ .…”

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Crystal Structure of Isothiocyanato-N,N'-dimethyl-N,N'-bis(pyridine-2-ylmethyl)propane-1,3-diaminecopper(II) Perchlorate

Yokoyama

Yoshise

HASE

et al. 2011

X-ray Structure Analysis Online

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The synthesis, electrochemistry, and reactivities of a complex cation, trans-dioxo-N,N¢-dimethyl-N,N¢-bis(pyridine-2-ylmethyl)propane-1,3-diamineruthenium(VI)(trans-[Ru(LMe2)O2] 2+ ), have been reported. 1 It can oxidize tetrahydrofuran and aromatic hydrocarbons under mild conditions. Its pyridine functional group increases both the redox potential and the reactivity of the ruthenium oxo oxidant. It is considered that its reactivity would also depend on the geometry of the pyridine functional group on the structure of the complex cation. The redox behaviors of [Cu(LMe2) N¢-dimethyl-N,N¢-bis(pyridine-2-ylmethyl)ethane-1,2-diamine (L¢Me2) and perchlorate ions has been also reported. 6 Only one perchlorate ion in [Cu(ClO4)(L¢Me2)]ClO4 coordinates to the Cu 2+ ion. Each N-methyl group of the [Cu(ClO4)(L¢Me2)]ClO4 is placed at a cis configuration. The crystal structures of manganese(II) and copper(II) with its L¢Me2 included in these binuclear complexes have been reported. 5,7 The pyridine functional group on the complex cation with an ethylene group between two N-pyridine-2-ylmethylamines would have a more rigid geometry than that with the propylene group. 8 The Cu-N4 square-planar geometry of [Cu(ClO4)2(LMe2)] is distorted more than that of N, N¢-bis(pyridine-2-ylmethyl) The complex of an isothiocyanato-N,N¢-dimethyl-N,N¢-bis(pyridine-2-ylmethyl)propane-1,3-diaminecopper(II) perchlorate ([Cu(NCS)(LMe2)]ClO4) was prepared. Its crystal structure was determined by X-ray diffractometry. [Cu(NCS)(LMe2)]ClO4 crystallized in a triclinic system, and was characterized thus: P1, a = 9.257(3), b = 9.883(4), c = 11.806(5)Å, a = 89.638(12), b = 81.053(10), g = 88.841(12)˚, Z = 2, V = 1066.7(7)Å 3 . The crystal structure was solved by direct methods and refined by full-matrix least squares on F 2 to final values of R1 = 0.058.

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confidence: 99%

“…The crystal structure of copper(II) with its analogous N,N¢-dimethyl-N,N¢-bis(pyridine-2-ylmethyl)ethane-1,2-diamine (L¢Me2) and perchlorate ions has been also reported. 6 Only one perchlorate ion in [Cu(ClO4)(L¢Me2)]ClO4 coordinates to the Cu 2+ ion. Each N-methyl group of the [Cu(ClO4)(L¢Me2)]ClO4 is placed at a cis configuration.…”

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confidence: 99%

Crystal Structure of Isothiocyanato-N,N'-dimethyl-N,N'-bis(pyridine-2-ylmethyl)propane-1,3-diaminecopper(II) Perchlorate

Yokoyama

Yoshise

HASE

et al. 2011

X-ray Structure Analysis Online

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“…2 Å). The mean Cu II –O (triflate) bond length computed from 128 hits in the CSD was approximately 2.55 Å, which confirmed that triflate ions were weakly bonded in C3 …”

Section: Resultsmentioning

confidence: 66%

Imidazolidine Ring Cleavage upon Complexation with First‐Row Transition Metals

et al. 2017

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The reaction of a cyclic diaminal ligand, obtained from the reaction of N,N′‐bis(2‐pyridylmethyl)ethane‐1,2‐diamine, as a secondary diamine, and isophthalaldehyde, with different first‐row transition‐metal ions, such as FeIII, ZnII, CuII, and CuI, was explored using UV/Vis kinetic studies, and cyclic voltammetry. The 3D structures of the resulting metal complexes were determined by single‐crystal X‐ray diffraction analysis. We demonstrate that the ring‐cleavage reaction of the imidazolidine ligand upon complexation with various metal ions depends on the Lewis acidity of the metal ions, as well as on the coordinative requirements of the metal centers. With a soft acid such as CuI, the diaminal ligand was unmodified and stabilized tricoordinate planar cuprous ions. In contrast, in the presence of harder acids, such as FeIII, ZnII, and CuII, the diaminal ligand undergoes hydrolysis/cleavage to yield complexes of the tetradentate N,N′‐bis(2‐pyridylmethyl)ethane‐1,2‐diamine ligand. Interestingly, it was also observed that the ring‐cleavage reaction in the presence of FeIII led to the formation of FeII complexes. However, we demonstrate that these two events are independent from each other.

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“…However, each the N-methyl groups for the perchlorate ioncoordinating [Cu(ClO4)2(LMe2)] was trans-configuration. 1 Therefore, the configuration did not only depend on the coordinating strength of anions, such as the weak coordinated pechlorate and the strong coordinated isothiocyanate ion. It is considered that it would depend on a concerted distortion of those Cu(II) complexes associated with a steric hindrance of the two N-alkyl groups in LRR' of a peripheral ligand with the coordinating strength of the coordinated anions.…”

Section: The Crystal Structures Of Nn¢-dimethyl-nn¢-bis(pyridin-2-ymentioning

confidence: 97%

“…perchlorate ([Cu(ClO4)2(LMe2)]) 1 and isothiocyanato-N,N¢-dimethyl-N,N¢-bis(pyridin-2-ylmethyl)propane-1,3-diaminecopper(II) perchlorate ([Cu(NCS)(LMe2)]ClO4) 2 have been reported. Each of the N-methyl groups is placed at a trans-and a cisconfiguration for [Cu(ClO4)2(LMe2)] and [Cu(NCS)(LMe2)]ClO4, respectively.…”

Section: The Crystal Structures Of Nn¢-dimethyl-nn¢-bis(pyridin-2-ymentioning

confidence: 99%

Crystal Structure of Catena-(μ2-perchlorato)-N-ethyl-N,N′-bis(pyridin-2-ylmethyl)propane-1,3-diaminecopper(II) Perchlorate

Yokoyama

Yoshise

HASE

et al. 2012

X-ray Structure Analysis Online

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The crystal structures of N, N¢-dimethyl-N,N¢-bis(pyridin-2-ylmethyl)propane-1,3-diaminecopper(II) perchlorate ([Cu(ClO4)2(LMe2)]) 1 and isothiocyanato-N,N¢-dimethyl-N,N¢-bis(pyridin-2-ylmethyl)propane-1,3-diaminecopper(II) perchlorate ([Cu(NCS)(LMe2)]ClO4) 2 have been reported. Each of the N-methyl groups is placed at a trans-and a cisconfiguration for [Cu(ClO4)2(LMe2)] and [Cu(NCS)(LMe2)]ClO4, respectively. When the two N-methyl groups were replaced at two N-ethyl groups, each of the N-ethyl groups for isothiocyanato-N,N¢-diethyl-N,N¢-bis(pyridin-2-ylmethyl)propane-1,3-diaminecopper(II) perchlorate ([Cu(NCS)(LEt2)] ClO4) was placed at the cis-configuration. 3 This would be one reason why a small distortion of the complex coordinated LMe2 or LEt2 and isothiocyanate or perchlorate ion to Cu(II) is more preferable to a large one. Therefore, the different configuration of N-alkyl groups, such as N-methyl and N-ethyl groups, depending on the distortion for analogous Cu(II) complexes, is interesting. The strong coordinating isothiocyanate ion to those Cu(II) complexes might cause the cis-configuration for the N-alkyl groups, while the weak coordinating perchlorate ion might cause the trans-configuration for them. Therefore, a crystal structure of the analogous Cu(II) complex, catena-(m2-

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DFT and Experimental Studies of Perchlorate Ion Coordination incis/trans‐Copper(II) Complexes of Tetradentate Pyridyl Ligands

Abstract: Spectral and structural studies of N, , where both NCH 3 groups are oriented in the same plane, is in equilibrium with its trans isomer and, as a result, a small energy difference (0.9 kcal mol -1 ) appears. In

Cited by 19 publications

References 61 publications

Crystal Structure of Isothiocyanato-N,N'-dimethyl-N,N'-bis(pyridine-2-ylmethyl)propane-1,3-diaminecopper(II) Perchlorate

Crystal Structure of Isothiocyanato-N,N'-dimethyl-N,N'-bis(pyridine-2-ylmethyl)propane-1,3-diaminecopper(II) Perchlorate

Imidazolidine Ring Cleavage upon Complexation with First‐Row Transition Metals

Crystal Structure of <i>Catena</i>-(<i>μ</i><sub>2</sub>-perchlorato)-<i>N</i>-ethyl-<i>N</i>,<i>N</i>′-bis(pyridin-2-ylmethyl)propane-1,3-diaminecopper(II) Perchlorate

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