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
N1 - Funding Information:
One of the authors (R.S.C) is grateful to DST for financial support under the DST young scientist scheme YSS/2014/000797. S.K.S acknowledges the Department of Science and Technology for the Start-up Research Grant (SRG/2020/001323) and IIT Hyderabad for generous funding. S.M. thanks Prime Minister Research Fellowship. Y.T. is grateful to the Ministry of Science and Higher Education of the Russian Federation for the support of XRD experiments performed at the experimental facilities supported by Kurnakov Institute of General and Inorganic
Funding Information:
One of the authors (R.S.C) is grateful to DST for financial support under the DST young scientist scheme YSS/2014/000797. S.K.S acknowledges the Department of Science and Technology for the Start-up Research Grant (SRG/2020/001323) and IIT Hyderabad for generous funding. S.M. thanks Prime Minister Research Fellowship. Y.T. is grateful to the Ministry of Science and Higher Education of the Russian Federation for the support of XRD experiments performed at the experimental facilities supported by Kurnakov Institute of General and Inorganic, Chemistry RAS. The support and resources provided by PARAM Shivay Facility under the National Supercomputing Mission, Government of India at the Indian Institute of Technology, Varanasi, are gratefully acknowledged.
Publisher Copyright:
© 2021
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
UR - http://www.scopus.com/inward/record.url?scp=85119430972&partnerID=8YFLogxK
U2 - 10.1016/j.jorganchem.2021.122177
DO - 10.1016/j.jorganchem.2021.122177
M3 - Article
AN - SCOPUS:85119430972
SN - 0022-328X
VL - 957
JO - Journal of Organometallic Chemistry
JF - Journal of Organometallic Chemistry
M1 - 122177
ER -