Repozytorium
Wyszukaj
Kolekcje
Inne
New substituents for the stabilization of low-coordinate germanium species: use in access to diazogermylenes.
Autorzy
Rok wydania
2010
Czasopismo
Numer woluminu
29
Strony
3269-3276
DOI
10.1016/j.poly.2010.08.039
Kolekcja
Język
Angielski
Typ publikacji
Artykuł
The reactions of the P-bis(trimethylsilyl)amino-N-(trimethylsilyl)iminophosphine with various dialkoxydichlorogermanes (alkoxy: OR = OMe, OEt and Oi-Pr) at 0 °C led to the stable dichlorogermylene-complexes [(RO)2P(NSiMe3)(N(SiMe3)2)]GeCl2 [R = Me (1), Et (2) and R = i-Pr (3)]. The solid-state structure of (2) has been determined by X-ray crystallography. A mechanism for the formation of these compounds is proposed, based on the transient species observed in the case of the isopropoxy derivatives. At room temperature in benzene solution, compounds (1) and (2) eliminate chlorotrimethylsilane without side reactions leading to the corresponding 2,4-diaza-3-phosphagermatidines [(RO)2P(NSiMe3)2]GeCl (4) and (5), respectively. At the opposite, complex (3) showed a modulated behavior: at room temperature, (3) still slowly eliminates mainly chlorotrimethylsilane with the formation of [(i-PrO)2P(NSiMe3)2]GeCl (6). Structure of this chlorinated germanium(II) compound which can also be seen as a germyl anion has been evidenced by an X-ray analysis. But at higher temperature (40–50 °C) (3) mainly decomposes with elimination of isopropylchloride leading to the formation of [(i-PrO)(Me3SiO)P(NSiMe3)2]GeCl (7) as a mixture of Z- and E-isomers. The mechanism of this reaction is discussed. The Z-isomer of (7) was successfully isolated after a selective crystallization, and investigated by an X-ray analysis. The interconversion mechanism of the two diastereoisomers is also discussed. Reaction of compound (5) with the lithio derivative of the trimethylsilyldiazomethane leads to the diazogermylene (8), a potential precursor of germa-alkyne.
Słowa kluczowe
Chlorinated germanium(II), Donor ligands, Mechanism, Diazogermylene
Adres publiczny
https://doi.org/10.1016/j.poly.2010.08.039
Strona internetowa wydawcy
Podobne publikacje
Dioxidovanadium(V) complexes containing thiazol-hydrazone NNN-donor ligands and their catalytic activity in the oxidation of olefins.
Ghorbanloo Massomeh, Jafari Solmaz, Bikas Rahman, Krawczyk Marta S., Lis Tadeusz
Mechanistic studies on the in-situ generation of furoxan ring during the formation of Cu(II) coordination compound from dioxime ligand : theoretical and experimental study.
Bikas Rahman, Valadbeigi Younes, Otręba Marta, Lis Tadeusz
Coordination chemistry of H‐spirophosphorane ligands towards pentacarbonylchlororhenium(I) : synthesis, structure and catalytic activity of complexes.
Skarżyńska Anna, Siczek Miłosz, Gawryszewska Paula, Chaczko Karolina