کد مقاله | کد نشریه | سال انتشار | مقاله انگلیسی | نسخه تمام متن |
---|---|---|---|---|
1326192 | 977420 | 2008 | 7 صفحه PDF | دانلود رایگان |
![عکس صفحه اول مقاله: Synthesis and derivatization of naphthylcalcium halides as well as degradation in THF solution Synthesis and derivatization of naphthylcalcium halides as well as degradation in THF solution](/preview/png/1326192.png)
The direct synthesis of 1-naphthyliodide and -bromide with calcium powder yields (thf)4Ca(Naph)I (1) and [(thf)3Ca(Naph)Br]2 (2), respectively. The metathesis reaction of 1 with KN(SiMe3)2 gives (thf)3Ca(Naph)–N(SiMe3)2 (3). In 2 and 3 very small Ca–C bond lengths of 252.8(4) and 251.4(6) pm, respectively, are observed. These compounds slowly decompose in THF solution via ether cleavage reactions. From this degradation, [(thf)4CaBr2] · naphthalene (4) crystallizes from THF solutions. Furthermore, decomposition of 1 in THF solution yields ethene and naphthalene whereas intermediate ethenolate undergoes subsequent degradation to an acetylide.
The direct synthesis of calcium powder with naphthylbromide yields [(thf)3Ca(Naph)Br]2 with bridging bromide anions whereas naphthylchloride shows no reactivity towards calcium. The bulky N(SiMe3)2 ligand leads to monomeric (thf)3Ca(Naph)–N(SiMe3) with strong agostic bonds between calcium and one trimethylsilyl group.Figure optionsDownload as PowerPoint slide
Journal: Journal of Organometallic Chemistry - Volume 693, Issue 2, 15 January 2008, Pages 221–227