Dinuclear CuII-CuII and CuI-Cu II complexes of a compartmental ligand - Syntheses, structures, magnetic, and catalytic studies

Surajit Biswas, Arpan Dutta, Malay Dolai, Indrani Bhowmick, Mathieu Rouzières, Hon Man Lee, Rodolphe Clérac, Mahammad Ali

Research output: Contribution to journalArticle

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Abstract

Dinuclear CuII-CuII (1) and CuI-Cu II (2) complexes were derived from a new N4O2 donor compartmental ligand (H2L) by changing the nature of the Cu precursors used. Single-crystal X-ray diffraction studies revealed that the Cu1 site in 1 has octahedral geometry and is in the inner compartment of the ligand axially coordinated by two ClO4- anions, whereas the outer Cu2 ion has square-pyramidal geometry. In 2, there are two copper dinuclear complexes (A and B) in the asymmetric unit; the inner core is occupied by Cu1/Cu3 in the +2 oxidation state in a square-planar geometry. The Cu2/Cu4 ion occupies the outer sites and has distorted tetrahedral geometry with a +1 oxidation state. Complexes 1 and 2 were obtained simply by changing Cu(ClO 4)2 in 1 to Cu(ClO4)2 and Cu(bipy)(NO3)2 in 2; the bipyridyl (bipy) ligand induces the reduction of CuII to CuI, which is trapped in the CuI-CuII dinuclear product. The oxidation states of the metal ions were ascertained from charge-balance considerations as well as from bond valence sum (BVS) calculations. No signature of intervalence charge transfer (IVCT) was observed by spectroscopy (UV/Vis/NIR) as well as from the low-temperature magnetic studies. This might be because of the presence of two copper centers in two different geometries with a wide separation between them (ca. 3.27 Å). For 1, the best fit of the χT vs. T data to the dimer model gives J/kB = -262(1) K and gav = 2.05(5), which indicates that there is a strong antiferromagnetic coupling between the two Cu atoms. In 2, the CuI center is diamagnetic and, thus, the remaining S = 1/2 CuII magnetic center follows a Curie law with g = 2.06(5). Under homogeneous conditions, both complexes showed catalytic epoxidation of cyclooctene, styrene, and norbornene to the corresponding epoxides with high selectivities and turnover numbers (TONs), which seem to be slightly better than the reported values for CuII Schiff base complexes. Dinuclear CuII-CuII (1) and CuI-CuII (2) complexes derived from a new N4O2 donor ligand (H 2L) are synthesized and characterized by single-crystal X-ray diffraction, UV/Vis spectroscopy, and magnetic measurements. In 1, there is strong antiferromagnetic coupling between the Cu atoms. In 2, the CuI ion is diamagnetic and the remaining S = 1/2 CuII magnetic center follows a Curie law with g = 2.06(5).

Original languageEnglish
Pages (from-to)4922-4930
Number of pages9
JournalEuropean Journal of Inorganic Chemistry
Issue number28
DOIs
Publication statusPublished - 2013 Oct 1

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Magnetic structure
Ligands
Geometry
2,2'-Dipyridyl
Ions
Ultraviolet spectroscopy
Oxidation
Copper
Single crystals
X ray diffraction
Atoms
Styrene
Epoxidation
Schiff Bases
Epoxy Compounds
Magnetic variables measurement
Dimers
Anions
Metal ions
Charge transfer

All Science Journal Classification (ASJC) codes

  • Inorganic Chemistry

Cite this

Biswas, Surajit ; Dutta, Arpan ; Dolai, Malay ; Bhowmick, Indrani ; Rouzières, Mathieu ; Lee, Hon Man ; Clérac, Rodolphe ; Ali, Mahammad. / Dinuclear CuII-CuII and CuI-Cu II complexes of a compartmental ligand - Syntheses, structures, magnetic, and catalytic studies. In: European Journal of Inorganic Chemistry. 2013 ; No. 28. pp. 4922-4930.
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title = "Dinuclear CuII-CuII and CuI-Cu II complexes of a compartmental ligand - Syntheses, structures, magnetic, and catalytic studies",
abstract = "Dinuclear CuII-CuII (1) and CuI-Cu II (2) complexes were derived from a new N4O2 donor compartmental ligand (H2L) by changing the nature of the Cu precursors used. Single-crystal X-ray diffraction studies revealed that the Cu1 site in 1 has octahedral geometry and is in the inner compartment of the ligand axially coordinated by two ClO4- anions, whereas the outer Cu2 ion has square-pyramidal geometry. In 2, there are two copper dinuclear complexes (A and B) in the asymmetric unit; the inner core is occupied by Cu1/Cu3 in the +2 oxidation state in a square-planar geometry. The Cu2/Cu4 ion occupies the outer sites and has distorted tetrahedral geometry with a +1 oxidation state. Complexes 1 and 2 were obtained simply by changing Cu(ClO 4)2 in 1 to Cu(ClO4)2 and Cu(bipy)(NO3)2 in 2; the bipyridyl (bipy) ligand induces the reduction of CuII to CuI, which is trapped in the CuI-CuII dinuclear product. The oxidation states of the metal ions were ascertained from charge-balance considerations as well as from bond valence sum (BVS) calculations. No signature of intervalence charge transfer (IVCT) was observed by spectroscopy (UV/Vis/NIR) as well as from the low-temperature magnetic studies. This might be because of the presence of two copper centers in two different geometries with a wide separation between them (ca. 3.27 {\AA}). For 1, the best fit of the χT vs. T data to the dimer model gives J/kB = -262(1) K and gav = 2.05(5), which indicates that there is a strong antiferromagnetic coupling between the two Cu atoms. In 2, the CuI center is diamagnetic and, thus, the remaining S = 1/2 CuII magnetic center follows a Curie law with g = 2.06(5). Under homogeneous conditions, both complexes showed catalytic epoxidation of cyclooctene, styrene, and norbornene to the corresponding epoxides with high selectivities and turnover numbers (TONs), which seem to be slightly better than the reported values for CuII Schiff base complexes. Dinuclear CuII-CuII (1) and CuI-CuII (2) complexes derived from a new N4O2 donor ligand (H 2L) are synthesized and characterized by single-crystal X-ray diffraction, UV/Vis spectroscopy, and magnetic measurements. In 1, there is strong antiferromagnetic coupling between the Cu atoms. In 2, the CuI ion is diamagnetic and the remaining S = 1/2 CuII magnetic center follows a Curie law with g = 2.06(5).",
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Dinuclear CuII-CuII and CuI-Cu II complexes of a compartmental ligand - Syntheses, structures, magnetic, and catalytic studies. / Biswas, Surajit; Dutta, Arpan; Dolai, Malay; Bhowmick, Indrani; Rouzières, Mathieu; Lee, Hon Man; Clérac, Rodolphe; Ali, Mahammad.

In: European Journal of Inorganic Chemistry, No. 28, 01.10.2013, p. 4922-4930.

Research output: Contribution to journalArticle

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T1 - Dinuclear CuII-CuII and CuI-Cu II complexes of a compartmental ligand - Syntheses, structures, magnetic, and catalytic studies

AU - Biswas, Surajit

AU - Dutta, Arpan

AU - Dolai, Malay

AU - Bhowmick, Indrani

AU - Rouzières, Mathieu

AU - Lee, Hon Man

AU - Clérac, Rodolphe

AU - Ali, Mahammad

PY - 2013/10/1

Y1 - 2013/10/1

N2 - Dinuclear CuII-CuII (1) and CuI-Cu II (2) complexes were derived from a new N4O2 donor compartmental ligand (H2L) by changing the nature of the Cu precursors used. Single-crystal X-ray diffraction studies revealed that the Cu1 site in 1 has octahedral geometry and is in the inner compartment of the ligand axially coordinated by two ClO4- anions, whereas the outer Cu2 ion has square-pyramidal geometry. In 2, there are two copper dinuclear complexes (A and B) in the asymmetric unit; the inner core is occupied by Cu1/Cu3 in the +2 oxidation state in a square-planar geometry. The Cu2/Cu4 ion occupies the outer sites and has distorted tetrahedral geometry with a +1 oxidation state. Complexes 1 and 2 were obtained simply by changing Cu(ClO 4)2 in 1 to Cu(ClO4)2 and Cu(bipy)(NO3)2 in 2; the bipyridyl (bipy) ligand induces the reduction of CuII to CuI, which is trapped in the CuI-CuII dinuclear product. The oxidation states of the metal ions were ascertained from charge-balance considerations as well as from bond valence sum (BVS) calculations. No signature of intervalence charge transfer (IVCT) was observed by spectroscopy (UV/Vis/NIR) as well as from the low-temperature magnetic studies. This might be because of the presence of two copper centers in two different geometries with a wide separation between them (ca. 3.27 Å). For 1, the best fit of the χT vs. T data to the dimer model gives J/kB = -262(1) K and gav = 2.05(5), which indicates that there is a strong antiferromagnetic coupling between the two Cu atoms. In 2, the CuI center is diamagnetic and, thus, the remaining S = 1/2 CuII magnetic center follows a Curie law with g = 2.06(5). Under homogeneous conditions, both complexes showed catalytic epoxidation of cyclooctene, styrene, and norbornene to the corresponding epoxides with high selectivities and turnover numbers (TONs), which seem to be slightly better than the reported values for CuII Schiff base complexes. Dinuclear CuII-CuII (1) and CuI-CuII (2) complexes derived from a new N4O2 donor ligand (H 2L) are synthesized and characterized by single-crystal X-ray diffraction, UV/Vis spectroscopy, and magnetic measurements. In 1, there is strong antiferromagnetic coupling between the Cu atoms. In 2, the CuI ion is diamagnetic and the remaining S = 1/2 CuII magnetic center follows a Curie law with g = 2.06(5).

AB - Dinuclear CuII-CuII (1) and CuI-Cu II (2) complexes were derived from a new N4O2 donor compartmental ligand (H2L) by changing the nature of the Cu precursors used. Single-crystal X-ray diffraction studies revealed that the Cu1 site in 1 has octahedral geometry and is in the inner compartment of the ligand axially coordinated by two ClO4- anions, whereas the outer Cu2 ion has square-pyramidal geometry. In 2, there are two copper dinuclear complexes (A and B) in the asymmetric unit; the inner core is occupied by Cu1/Cu3 in the +2 oxidation state in a square-planar geometry. The Cu2/Cu4 ion occupies the outer sites and has distorted tetrahedral geometry with a +1 oxidation state. Complexes 1 and 2 were obtained simply by changing Cu(ClO 4)2 in 1 to Cu(ClO4)2 and Cu(bipy)(NO3)2 in 2; the bipyridyl (bipy) ligand induces the reduction of CuII to CuI, which is trapped in the CuI-CuII dinuclear product. The oxidation states of the metal ions were ascertained from charge-balance considerations as well as from bond valence sum (BVS) calculations. No signature of intervalence charge transfer (IVCT) was observed by spectroscopy (UV/Vis/NIR) as well as from the low-temperature magnetic studies. This might be because of the presence of two copper centers in two different geometries with a wide separation between them (ca. 3.27 Å). For 1, the best fit of the χT vs. T data to the dimer model gives J/kB = -262(1) K and gav = 2.05(5), which indicates that there is a strong antiferromagnetic coupling between the two Cu atoms. In 2, the CuI center is diamagnetic and, thus, the remaining S = 1/2 CuII magnetic center follows a Curie law with g = 2.06(5). Under homogeneous conditions, both complexes showed catalytic epoxidation of cyclooctene, styrene, and norbornene to the corresponding epoxides with high selectivities and turnover numbers (TONs), which seem to be slightly better than the reported values for CuII Schiff base complexes. Dinuclear CuII-CuII (1) and CuI-CuII (2) complexes derived from a new N4O2 donor ligand (H 2L) are synthesized and characterized by single-crystal X-ray diffraction, UV/Vis spectroscopy, and magnetic measurements. In 1, there is strong antiferromagnetic coupling between the Cu atoms. In 2, the CuI ion is diamagnetic and the remaining S = 1/2 CuII magnetic center follows a Curie law with g = 2.06(5).

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