Mercapto derivatives of triorganotin Y,C,Y-pincer complexes: Role of Y,C,Y-chelating ligands in a new coordination mode of organotin compounds
- 作者：Jana Martincová ; Libor Dostá ; l ; Jan Taraba ; Aleš ; Rů ; ž ; ič ; ka ; Roman Jambor
- 关键词：Organotin ; Chelating ligands ; NMR ; Crystal structure
- 刊名：Journal of Organometallic Chemistry
- 出版年：2007
- 期刊代码：64_0022328x
- 类别：ch
- 出版时间：15 July 2007
- 卷：692
- 期：16
- 页码：3415-3423
- 文件大小：421 K
摘要
We report the use of triorganotin fragments R<sub>2sub>L<sup>1-2sup>Sn containing N,C,N and O,C,O-ligands L<sup>1-2sup>(L<sup>1sup> = C<sub>6sub>H<sub>3sub>(Me<sub>2sub>NCH<sub>2sub>)<sub>2sub>-2,6<sup>−sup>, L<sup>2sup> = C<sub>6sub>H<sub>3sub>(<sup>tsup>BuOCH<sub>2sub>)<sub>2sub>-2,6<sup>−sup>) on stabilization of both thiol-form in R<sub>2sub>L<sup>1-2sup>Sn-2-SPy (2-SPy = pyridine-2-thiolate) and thione-form in R<sub>2sub>L<sup>1-2sup>Sn(mimt) (mimt = 1-methylimidazole-2-thiolate) of the polar groups. Treatment of ionic organotin compounds [Me<sub>2sub>L<sup>1sup>Sn]<sup>+sup>[Cl]<sup>−sup> (<strong>1strong>) and [Ph<sub>2sub>L<sup>2sup>Sn]<sup>+sup>[OTf]<sup>−sup> (<strong>2strong>) with appropriate sodium salts Na-2-SPy and Na(mimt) resulted in the isolation of Me<sub>2sub>L<sup>1sup>Sn-2-SPy (<strong>3strong>), Ph<sub>2sub>L<sup>2sup>Sn-2-SPy (<strong>4strong>), Me<sub>2sub>L<sup>1sup>Sn(mimt) (<strong>5strong>), Ph<sub>2sub>L<sup>2sup>Sn(mimt) (<strong>6strong>). While polar group 2-SPy exists in its thiol-tautomeric form in compounds <strong>3strong> and <strong>4strong>, the second polar group (mimt) has been stabilized as the thione-tautomeric form by triorganotin fragments R<sub>2sub>L<sup>1-2sup>Sn in compounds <strong>5strong> and <strong>6strong>. The products were characterized by <sup>1sup>H, <sup>13sup>C and <sup>119sup>Sn NMR and IR spectroscopy, ESI/MS, elemental analyses and structures of <strong>3strong>, <strong>6strong> were determined by X-ray diffraction study. The reactivity of compound <strong>4strong> containing non-coordinated nitrogen atom of 2-SPy polar group towards CuCl and AgNO<sub>3sub> is also reported. The reactions led to isolation of organotin compounds Ph<sub>2sub>L<sup>2sup>SnCl (<strong>7strong>) and Ph<sub>2sub>L<sup>2sup>SnNO<sub>3sub> (<strong>8strong>) as the result of polar group transfer. The mechanism of this reaction has been investigated and compounds Ph<sub>3sub>Sn-2-SPy (<strong>9strong>) and Ph<sub>2sub>L<sup>2sup>Sn-4-SPy (<strong>10strong>) (4-SPy = pyridine-4-thiolate) have been prepared for this purpose.