Details

Autor(en) / Beteiligte

• Zhang, Shu-Hua
• Xi, Hong-Wei
• Lim, Kok Hwa
• Meng, Qingyong
• Huang, Ming-Bao
• So, Cheuk-Wai

Titel

Synthesis and Characterization of a Singlet Delocalized 2,4-Diimino-1,3-disilacyclobutanediyl and a Silylenylsilaimine

Ist Teil von

• Chemistry : a European journal, 2012-04, Vol.18 (14), p.4258-4263

Ort / Verlag

Weinheim: WILEY-VCH Verlag

Erscheinungsjahr

2012

Quelle

Wiley Online Library - AutoHoldings Journals

Beschreibungen/Notizen

• The synthesis and characterization of a singlet delocalized 2,4‐diimino‐1,3‐disilacyclobutanediyl, [LSi(μ‐CNAr)2SiL] (2, L: PhC(NtBu)2, Ar: 2,6‐iPr2C6H3), and a silylenylsilaimine, [LSi(NAr)SiL] (3), are described. The reaction of three equivalents of the disilylene [LSiSiL] (1) with two equivalents of ArNCNAr in toluene at room temperature for 12 h afforded [LSi(μ‐CNAr)2SiL] (2) and [LSi(NAr)SiL] (3) in a ratio of 1:2. Compounds 2 and 3 have been characterized by NMR spectroscopy and X‐ray crystallography. Compound 2 was also investigated by theoretical studies. The results show that compound 2 possesses singlet biradicaloid character with an extensive electronic delocalization throughout the Si2C2 four‐membered ring and exocyclic CN bonds. Compound 3 is the first example of a silylenylsilaimine, which contains a low‐valent silicon center and a silaimine substituent. A mechanism for the formation of 2 and 3 is also proposed. Spreading the radical: The reaction of three equivalents of 1 with two equivalents of ArNCNAr in toluene at room temperature afforded 2 and 3 (see scheme). Compound 2 possesses singlet biradicaloid character with an extensive electronic delocalization throughout the Si2C2 four‐membered ring and exocyclic CN bonds. Compound 3 is a silylenylsilaimine, which contains a low‐valent silicon center and a silaimine substituent.