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

Chauhan, Rohit Singh and Moorthy, Shruti and Tyagi, Adish and Torubaev, Yury and Butcher, Raymond J. and Singh, Saurabh Kumar (2022) Solvent mediated synthesis of homoleptic tri and tetranuclear nickel complex derived from [Ni2(µ-SeC5H4N)2(dppe)2]2+ and theoretical studies. Journal of Organometallic Chemistry, 957. pp. 1-11. ISSN 0022-328X

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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. © 2021

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IITH Creators:

IITH Creators	ORCiD
Singh, Saurabh Kumar	UNSPECIFIED

Item Type:

Article

Additional 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

Uncontrolled Keywords:

DFT; Nickel seleonate; Single crystal X-ray

Subjects:

Chemistry

Divisions:

Department of Chemistry

Depositing User:

. LibTrainee 2021

Date Deposited:

28 Jul 2022 12:48

Last Modified:

28 Jul 2022 12:48