Publication detail

Unusual Reactivity of a C,N-Chelated Stannylene with Siloxanes and Silanols

Year: 2013

Type of publication: článek v odborném periodiku

Name of source: Organometallics

Publisher name: American Chemical Society

Place: Washington

Page from-to: 2398-2405

Titles:

Language	Name	Abstract	Keywords
cze	Neobvyklá reaktivita C,N-chelatovaného tannylenu se siloxany a silanoly	Reaktivita stannylenu (L-CN)(2)Sn (1), kde L-CN je 2-N,N-dimethylaminomethyl)fenyl substituent, s (2,2,6,6-tetramethylpiperidin-1-yl)oxyl (TEMPO), silikonovým tukem, a triphenylsilanoly byl prozkoumána. Reakce 1 s jedním ekvivalentem TEMPO a silikonovým tukem poskytuje cyklo-[(L-CN)(2)SnOSn(L-CN)(2)OSiMe2O] (6a), zatímco přídavek dvou ekvivalentů TEMPO poskytl cyklo-[(L-CN)(L-CN-O)SnOSiMe2OSiMe2O] (6b), v kterém atom dusíku z aminu jednoho z L-CN ligandů je oxidován na N-oxid. Reakce 1 s jedním ekvivalentem TEMPO a následující přídavek triphenylsilanolu poskytl (L-CN)(2)Sn(OSiPh3)(2) (5), který dále reagoval se vzduchem v chloroformu až na [(L-CN)(L-CN=O)Sn(OSiPh3)Cl] (7), obsahující jeden z chelatujících L-CN ligandů v odpovídající N-oxid formě. Na rozdíl od tohoto, přímá reakce 1 s jedením nebo dvěmi ekvivalenty triphenylsilanolu poskytla adukt [Sn-(OSiPh3)(2)] C6H5CH2NMe2 (8a) a iontovou sloučeninu [C6H5CH2N(H)Me-2](+)[Sn(OSiPh3)(3)](-)(8b). Všechny sloučeniny byly charakterizovány pomocí NMR spektroskopie a rentgenové difrakce. Analogické reakce 1 s aktivovanou silikou byly provedeny za vzniku cínem dopovanou silikou, která byla charakterizována práškovou rentgenovou difrakcí a různými spektroskopickými a mikroskopickými technikami.	krystalová struktura; transesterifikační reakce; NMR; C,N-chelatovaný tannylen; siloxany; silanoly
eng	Unusual Reactivity of a C,N-Chelated Stannylene with Siloxanes and Silanols	The reactivity of stannylene (L-CN)(2)Sn (1), where L-CN is the 2-(N,N-dimethylaminomethyl)phenyl substituent, toward (2,2,6,6-tetramethylpiperidin-1-yl)oxyl (TEMPO), silicon grease, and triphenylsilanol was explored. The reaction of 1 with one equivalent of TEMPO and silicon grease yielded cyclo-[(L-CN)(2)SnOSn(L-CN)(2)OSiMe2O] (6a), whereas the addition of two equivalents of TEMPO afforded cyclo-[(L-CN)(L-CN-O)SnOSiMe2OSiMe2O] (6b), in which the amine nitrogen atom of one of the L-CN ligands is oxidized to N-oxide. The reaction of 1 with one equivalent of TEMPO and subsequent addition of triphenylsilanol gave (L-CN)(2)Sn(OSiPh3)(2) (5), which further reacted with air in a chloroform solution to provide [(L-CN)(L-CN=O)Sn(OSiPh3)Cl] (7), containing one of the chelating L-CN ligands in the corresponding N-oxide form. In contrast, the direct reactions of 1 with one or two equivalents of triphenylsilanol gave rise to the adduct [Sn-(OSiPh3)(2)]center dot C6H5CH2NMe2 (8a) and the salt [C6H5CH2N(H)Me-2](+)[Sn(OSiPh3)(3)](-)(8b), respectively. All compounds were characterized by NMR spectroscopy and by X-ray diffraction. Analogous reactions of 1 with activated silica were shown to yield tin-doped silica, which was characterized by powder X-ray diffraction and various spectroscopic and microscopic techniques.	molecular-structure; crystal-structure; transesterification reactions; tricyclic stannasiloxane; dimethyl carbonate; ring size; silica; catalysts; nmr; polymerization

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