Synthesis of ONO‐Ligated Tetrylenes Based on 2,6‐bis(2‐Hydroxyphenyl)pyridines: Influence of Ligand Sterics on the Structure of the Products

• Published in: European journal of inorganic chemistry Vol. 26; no. 11
• Main Authors: Mankaev, Badma N., Serova, Valeriia A., Syroeshkin, Mikhail A., Akyeva, Anna Ya, Sobolev, Alexey V., Churakov, Andrei V., Lermontova, Elmira Kh, Minyaev, Mikhail E., Oprunenko, Yury F., Zabalov, Maxim V., Zaitsev, Kirill V., Zaitseva, Galina S., Karlov, Sergey S.
• Format: Journal Article
• Language: English
• Published: WEINHEIM Wiley 11.04.2023; Wiley Subscription Services, Inc
• Subjects: Acetonitrile; Chemistry; Chemistry, Inorganic & Nuclear; Coordination polymers; Electronic structure; Germanium; Glassy carbon; Inorganic chemistry; Ligand effects; Ligands; Lithium; Metathesis; Mossbauer spectroscopy; NMR spectroscopy; Physical Sciences; Pyridines; Reaction products; Science & Technology; Structure elucidation; Tin; Voltammetry; BIVALENT GERMANIUM; CRYSTAL-STRUCTURE; DENSITY; Electronic structure; Tin; Germanium; Ligand effects; RING-OPENING POLYMERIZATION; BASIS-SETS; SN; SPECTRA; Structure elucidation; METAL-COMPLEXES; LEAD COMPOUNDS
• ISSN: 1434-1948; 1099-0682
• DOI: 10.1002/ejic.202200690

A series of novel tetrylenes based on three 2,6‐bis(2‐hydroxyphenyl)pyridines 4 a–4 c have been obtained by the reaction of Lappert's tetrylenes E[N(SiMe3)2]2 (E=Ge, Sn) with corresponding tridentate pyridine‐linked phenol‐based ligands. It was found that the structure of the ligand and the size of the atom of the group 14 element drastically affect the structure of the reaction product. Ligand 4 c with a bulky tert‐butyl group leads to monomeric tetrylenes, while ligands with less bulky groups lead to bis‐ligand derivatives of M(IV) (M=Ge, Sn) and a coordination polymer. Also, derivatives of germanium (IV) and tin (IV) were obtained by the metathesis reaction of MCl4 (M=Ge, Sn) with lithium phenoxides. The compositions and structures of the novel compounds were established by elemental analysis and 1H, 13C, 119Sn (5–7), 1H DOSY (6) NMR spectroscopy, in the solid state by X‐ray diffraction analysis (germylene 10, stannylene 6, Ge4+ compound 8, Sn4+ compound 7) and 119Sn Mössbauer spectrum of tin complex 6. All the synthesized tetrylenes are monomeric. Tetrylenes 6 and 10 were characterized by cyclic voltammetry. A study of the redox behavior of 6, 10 by cyclic voltammetry on a glassy carbon working electrode in acetonitrile solution of 0.1 M Bu4NPF6 as a supporting electrolyte showed that these compounds can be both oxidized and reduced electrochemically in the accessible potential range. Tetrylenes based on substituted 2,6‐bis(2‐hydroxyphenyl)pyridines have been obtained. The dramatic influence of the ligand structure on the reaction pathways of free ligands with Lappert's tetrylenes has been established. Only sterically bulky ligands lead to the formation of monomeric tetrylenes.