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Intramolecularly O,N,O-Coordinated Tin(II) Salts: Syntheses, Structures, Cyclization, and Transition Metal Complexation
Autoři: Alnasr Hazem | Mross David | Platzek Andre | Nayyar Bastian | Řičica Tomáš | Schollmeyer Dieter | Jambor Roman | Hoffmann Alexander | Jurkschat Klaus
Rok: 2024
Druh publikace: článek v odborném periodiku
Název zdroje: Chemistry - A European Journal
Název nakladatele: Wiley-VCH
Místo vydání: Weinheim
Strana od-do: e202400580
Tituly:
Jazyk Název Abstrakt Klíčová slova
cze Intramolekulárné O,N,O-koordinované Sn(II) ionty Byly připravené intramolekulárné O,N,O-koordinované Sn(II) ionty a byly studované jejich cyklizace a koordinace na přechodné kovy. Intramolekulárné; O,N,O-koordinované; SnII; ionty
eng Intramolecularly O,N,O-Coordinated Tin(II) Salts: Syntheses, Structures, Cyclization, and Transition Metal Complexation We report the syntheses of tin(II) salts of the types [L1SnX]SnX3 [L1=2,6-{(i-PrO)2(O)P}2C5H3N: 1, X=Cl; 2, X=Br], [L2SnCl]SnCl3 [L2=2-{(i-PrO)Ph(O)P}-6-{(i-PrO)2(O)P}C5H3N: 3], [L3SnX]SnX3 [L3=2,6-{MeO(O)C}2C5H3N: 4, X=Cl; 5, X=Br], [L4SnX]SnX3 [L4=2,6-{Et2N(O)C}2C5H3N: 6, X=Cl; 7, X=Br]. These compounds were obtained by addition of SnX2 to the corresponding ligand inducing autoionization of the respective tin(II) halide. The thermal stability of 1, 3, and 4 was elucidated, giving, under ester cleavage and cyclisation, the tin(II) derivatives 8-12. The reaction of [L1SnCl]SnCl3 (1) with W(CO)4(thf)2 afforded the tungsten tetracarbonyl complex [{L1SnCl}{SnCl3}W(CO)4] (13), representing the first example in which a tin(II) stannate anion and a tin(II) stannylium cation simultaneously coordinate to a transition metal centre. The compounds were characterized by single crystal X-ray diffraction analyses and in part by elemental analyses, IR and NMR spectroscopy, electrospray ionization mass spectrometry. DFT calculations accompany the experimental work. Pyridine derivatives Ln containing phosphonyl, phosphinyl, carbonic ester, and carbonic amide type substituents in 2,6-positions induce autoionization of tin(II) halides giving pairs of intramolecularly O,N,O-coordinated [LnSnX]+ cations and SnX3- anions. These undergo thermally induced ester cleavage giving Sn(II) heterocycles containing stereogenic centres, and proved suitable as ligands toward W(CO)4. image Tin cation; X-ray diffraction; tungsten tetracarbonyl complex; DFT calculations; ester cleavage