Polyhedral phenylnickelsodiumsiloxanolate transformation in the presence of aromatic nitrogen-containing ligands

• Published in: Inorganica Chimica Acta 2021-03, Vol.517, p.120160, Article 120160
• Main Authors: Anisimov, Anton A., Vysochinskaya, Yulia S., Kononevich, Yuriy N., Dolgushin, Fedor M., Muzafarov, Aziz M., Shchegolikhina, Olga I.
• Format: Article
• Language: English
• Subjects: Cations; Ligands; Nickel; Recrystallization; Siloxanes; Sodium
• ISSN: 0020-1693; 1873-3255
• DOI: 10.1016/j.ica.2020.120160

[Display omitted] •Two new polyhedral phenylmetallasiloxane complexes , (1) and (2) formed in the process of recrystallization of polyhedral phenylnickelsodiumsiloxane (A) from DMF in the presence of 2,2-bipyridine (complex 1) or from pyridine (complex 2) are described.•It is found that σ-donor ligands of the pyridine series (pyridine and 2,2-bipyridine) play the crucial role in the process of dissociation of the initial metallasiloxane framework and its reassembly on a new matrix of metal ions.•Not only the metal-containing cationic layer is reconstructed with a change in the number, ratio, and spatial arrangement of nickel and sodium cations, but also changes the size of cyclic siloxane ligands. Two new polyhedral phenylmetallasiloxane complexes, {[PhSi(O)O−]6(Ni2+)6(Na+)2(μ3-OH)2[PhSi(O)O−]6}•2(BIPY)•4(DMF) (1) and {[PhSi(O)O−]6(Ni2+)3(Na+)6(μ5-OH)2[PhSi(O)O−]5}•7(PY)•2(n-BuOH)•2(H2O) (2) formed in the process of recrystallization of polyhedral phenylnickelsodiumsiloxane (Na+)2{[PhSi(O)O−]6(Ni2+)4(Na+)4(μ3-OH)2[PhSi(O)O−]6}•16(n-BuOH) (A) from DMF in the presence of 2,2-bipyridine (complex 1) or from pyridine (complex 2) are described. It is found that σ-donor ligands of the pyridine series (pyridine and 2,2-bipyridine) play a crucial role in the process of dissociation of the initial metallasiloxane framework and its reassembly on a new matrix of metal ions. Not only the metal-containing cationic layer is reconstructed with a change in the number, ratio, and spatial arrangement of nickel and sodium cations, but also changes the size of cyclic siloxane ligands.