Publikace detail

Intramolecularly O,N,O-Coordinated Tin(II) Salts: Syntheses, Structures, Cyclization, and Transition Metal Complexation

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

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