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Repozytorium publikacji
Politechniki Gdańskiej

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Crystal and electronic structures of Ni(II) silanethiolates containing flexible diamine ligands

Five nickel(II) complexes containing aliphatic diamines and tri-tert-butoxysilanethiolate ligand have been synthesized for the purpose of studying their structural, spectral (IR, UV–Vis, HF EPR) and thermal properties. Complexes (1)–(5) have been prepared in high yield by reactions of [Ni{SSi(OtBu)3}2(NH3)(H2O)] with 1.3-propanediamine (L1), 1,6-hexanediamine (L2), or 1,7-heptanediamine (L3). The X-ray structures were determined for complexes [Ni{(SSi(OtBu)3}2(μ-L1)2] (1), [Ni{(SSi(OtBu)3}2(μ-L2)2]n (2) and [Ni{(SSi(OtBu)3}2(μ-L3)4]n (3). Compound (1) is mononuclear with Ni(II) ions coordinated by two molecules of chelating 1.3-diaminepropane. Complexes (2) and (3) consist of 1D polymeric structures with Ni(II) atoms bridged by diamine molecules. The coordinated atoms and the nickel atom form a NiN2S2 square-planar core in polymeric (2) and a distorted trans-octahedral NiN4S2 core in mononuclear (1) and polynuclear (3). Reactions of [Ni{SSi(OtBu)3}2(NH3)(H2O)] with 1,4-butanediamine (L4) and 1,5-pentanediamine (L5) resulted in single crystals of compounds (4) and (5) which were not suitable for X-ray measurements. The spin Hamiltonian parameters g, D, and E were determined for compound (1) from high-field HF EPR spectra.

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