Solvent mediated synthesis of homoleptic tri and tetranuclear nickel complex derived from [Ni2(µ-SeC5H4N)2(dppe)2]2+ and theoretical studies

Rohit Singh Chauhan; Shruti Moorthy; Adish Tyagi; Yury Torubaev; Raymond J. Butcher; Saurabh Kumar Singh

doi:https://doi.org/10.1016/j.jorganchem.2021.122177

Solvent mediated synthesis of homoleptic tri and tetranuclear nickel complex derived from [Ni₂(µ-SeC₅H₄N)₂(dppe)₂]²⁺ and theoretical studies

Rohit Singh Chauhan, Shruti Moorthy, Adish Tyagi, Yury Torubaev, Raymond J. Butcher, Saurabh Kumar Singh

Research output: Contribution to journal › Article › peer-review

Abstract

In the present report, the reactivity of the binuclear complex [Ni₂(µ-SeC₅H₄N)₂(dppe)₂]²⁺ towards dichloromethane and methanol has been studied. The complex [Ni₂(µ-SeC₅H₄N)₂(dppe)₂]²⁺ in the presence of chlorinated solvent resulted in selenido bridged trinuclear complex of composition [Ni₃(µ-Se)₂(dppe)₂]²⁺ (1) whereas in the presence of methanol hydrolyzed product having cubane core [Ni₄{(C₅H₄N)₂Se}₄(μ_3[sbnd]OH)₄(C₆H₅COO)(HCOO)]²⁺ (2) was isolated. Both the complexes were characterized by elemental analysis, IR, ¹H, and ³¹P{¹H} NMR spectroscopy. An attempt has also been made to investigate their thermal studies. The molecular structure of both the complex [Ni₃(µ-Se)₂(dppe)₂]²⁺ (1) and [Ni₄{(C₅H₄N)₂Se}₄(μ_3[sbnd]OH)₄(C₆H₅COO)(HCOO)]²⁺ (2) were established by single-crystal X-ray diffraction analysis. Broken-symmetry density functional theory (BS-DFT) calculations were carried out on complex 2 to investigate the electronic structure and nature of magnetic exchange interaction. BS-DFT reveals the existence of three different J values i.e. -8.9 cm⁻¹, +18.7 cm⁻¹ and +1.8 cm⁻¹ between different Ni(II) pairs. A strong ferromagnetic interaction was observed between formate/phenylacetate bridged Ni(II) centers. An antiferromagnetic interaction between the ferromagnetically coupled formate and phenylacetate bridged Ni(II) dimers result in isolation of S = 0 spin ground state for complex 2. Molecular orbital, spin-density analyses were performed on the X-ray and optimized geometries to probe the electronic structure of complex 2.

Original language	American English
Article number	122177
Journal	Journal of Organometallic Chemistry
Volume	957
DOIs	https://doi.org/10.1016/j.jorganchem.2021.122177
State	Published - 1 Jan 2022
Externally published	Yes

Keywords

DFT
Nickel seleonate
Single crystal X-ray

All Science Journal Classification (ASJC) codes

Biochemistry
Physical and Theoretical Chemistry
Organic Chemistry
Inorganic Chemistry
Materials Chemistry

Access to Document

https://doi.org/10.1016/j.jorganchem.2021.122177

Cite this

@article{b377222dafb84e3dbcb4657f80991234,

title = "Solvent mediated synthesis of homoleptic tri and tetranuclear nickel complex derived from [Ni2(µ-SeC5H4N)2(dppe)2]2+ and theoretical studies",

abstract = "In the present report, the reactivity of the binuclear complex [Ni2(µ-SeC5H4N)2(dppe)2]2+ towards dichloromethane and methanol has been studied. The complex [Ni2(µ-SeC5H4N)2(dppe)2]2+ in the presence of chlorinated solvent resulted in selenido bridged trinuclear complex of composition [Ni3(µ-Se)2(dppe)2]2+ (1) whereas in the presence of methanol hydrolyzed product having cubane core [Ni4{(C5H4N)2Se}4(μ3[sbnd]OH)4(C6H5COO)(HCOO)]2+ (2) was isolated. Both the complexes were characterized by elemental analysis, IR, 1H, and 31P{1H} NMR spectroscopy. An attempt has also been made to investigate their thermal studies. The molecular structure of both the complex [Ni3(µ-Se)2(dppe)2]2+ (1) and [Ni4{(C5H4N)2Se}4(μ3[sbnd]OH)4(C6H5COO)(HCOO)]2+ (2) were established by single-crystal X-ray diffraction analysis. Broken-symmetry density functional theory (BS-DFT) calculations were carried out on complex 2 to investigate the electronic structure and nature of magnetic exchange interaction. BS-DFT reveals the existence of three different J values i.e. -8.9 cm−1, +18.7 cm−1 and +1.8 cm−1 between different Ni(II) pairs. A strong ferromagnetic interaction was observed between formate/phenylacetate bridged Ni(II) centers. An antiferromagnetic interaction between the ferromagnetically coupled formate and phenylacetate bridged Ni(II) dimers result in isolation of S = 0 spin ground state for complex 2. Molecular orbital, spin-density analyses were performed on the X-ray and optimized geometries to probe the electronic structure of complex 2.",

keywords = "DFT, Nickel seleonate, Single crystal X-ray",

author = "Chauhan, {Rohit Singh} and Shruti Moorthy and Adish Tyagi and Yury Torubaev and Butcher, {Raymond J.} and Singh, {Saurabh Kumar}",

note = "Publisher Copyright: {\textcopyright} 2021",

year = "2022",

month = jan,

day = "1",

doi = "https://doi.org/10.1016/j.jorganchem.2021.122177",

language = "American English",

volume = "957",

journal = "Journal of Organometallic Chemistry",

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TY - JOUR

T1 - Solvent mediated synthesis of homoleptic tri and tetranuclear nickel complex derived from [Ni2(µ-SeC5H4N)2(dppe)2]2+ and theoretical studies

AU - Chauhan, Rohit Singh

AU - Moorthy, Shruti

AU - Tyagi, Adish

AU - Torubaev, Yury

AU - Butcher, Raymond J.

AU - Singh, Saurabh Kumar

PY - 2022/1/1

Y1 - 2022/1/1

N2 - In the present report, the reactivity of the binuclear complex [Ni2(µ-SeC5H4N)2(dppe)2]2+ towards dichloromethane and methanol has been studied. The complex [Ni2(µ-SeC5H4N)2(dppe)2]2+ in the presence of chlorinated solvent resulted in selenido bridged trinuclear complex of composition [Ni3(µ-Se)2(dppe)2]2+ (1) whereas in the presence of methanol hydrolyzed product having cubane core [Ni4{(C5H4N)2Se}4(μ3[sbnd]OH)4(C6H5COO)(HCOO)]2+ (2) was isolated. Both the complexes were characterized by elemental analysis, IR, 1H, and 31P{1H} NMR spectroscopy. An attempt has also been made to investigate their thermal studies. The molecular structure of both the complex [Ni3(µ-Se)2(dppe)2]2+ (1) and [Ni4{(C5H4N)2Se}4(μ3[sbnd]OH)4(C6H5COO)(HCOO)]2+ (2) were established by single-crystal X-ray diffraction analysis. Broken-symmetry density functional theory (BS-DFT) calculations were carried out on complex 2 to investigate the electronic structure and nature of magnetic exchange interaction. BS-DFT reveals the existence of three different J values i.e. -8.9 cm−1, +18.7 cm−1 and +1.8 cm−1 between different Ni(II) pairs. A strong ferromagnetic interaction was observed between formate/phenylacetate bridged Ni(II) centers. An antiferromagnetic interaction between the ferromagnetically coupled formate and phenylacetate bridged Ni(II) dimers result in isolation of S = 0 spin ground state for complex 2. Molecular orbital, spin-density analyses were performed on the X-ray and optimized geometries to probe the electronic structure of complex 2.

AB - In the present report, the reactivity of the binuclear complex [Ni2(µ-SeC5H4N)2(dppe)2]2+ towards dichloromethane and methanol has been studied. The complex [Ni2(µ-SeC5H4N)2(dppe)2]2+ in the presence of chlorinated solvent resulted in selenido bridged trinuclear complex of composition [Ni3(µ-Se)2(dppe)2]2+ (1) whereas in the presence of methanol hydrolyzed product having cubane core [Ni4{(C5H4N)2Se}4(μ3[sbnd]OH)4(C6H5COO)(HCOO)]2+ (2) was isolated. Both the complexes were characterized by elemental analysis, IR, 1H, and 31P{1H} NMR spectroscopy. An attempt has also been made to investigate their thermal studies. The molecular structure of both the complex [Ni3(µ-Se)2(dppe)2]2+ (1) and [Ni4{(C5H4N)2Se}4(μ3[sbnd]OH)4(C6H5COO)(HCOO)]2+ (2) were established by single-crystal X-ray diffraction analysis. Broken-symmetry density functional theory (BS-DFT) calculations were carried out on complex 2 to investigate the electronic structure and nature of magnetic exchange interaction. BS-DFT reveals the existence of three different J values i.e. -8.9 cm−1, +18.7 cm−1 and +1.8 cm−1 between different Ni(II) pairs. A strong ferromagnetic interaction was observed between formate/phenylacetate bridged Ni(II) centers. An antiferromagnetic interaction between the ferromagnetically coupled formate and phenylacetate bridged Ni(II) dimers result in isolation of S = 0 spin ground state for complex 2. Molecular orbital, spin-density analyses were performed on the X-ray and optimized geometries to probe the electronic structure of complex 2.

KW - DFT

KW - Nickel seleonate

KW - Single crystal X-ray

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M3 - Article

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