Reactivity of the Donor-Stabilized Guanidinatosilylene [ArNC(NMe2)­NAr]Si[N(SiMe3)2] (Ar = 2,6-Diiso­propylphenyl)

• Published in: European journal of inorganic chemistry Vol. 2016; no. 11; pp. 1660 - 1670
• Main Authors: Mück, Felix M., Baus, Johannes A., Ulmer, Anna, Burschka, Christian, Tacke, Reinhold
• Format: Journal Article
• Language: English
• Published: Weinheim WILEY-VCH Verlag 01-04-2016; WILEY‐VCH Verlag
• Subjects: Carbon dioxide; Coordination chemistry; Correlation; Diffraction; Dipping; Joining; Lewis acid; Lewis acids; Lewis bases; Ligands; N ligands; Oxidation; Silicon; Silylenes; X-rays
• ISSN: 1434-1948; 1099-0682
• DOI: 10.1002/ejic.201600099

To get more information about the reactivity profile of the donor‐stabilized guanidinatosilylene [ArNC(NMe2)NAr]Si[N(SiMe3)2] (1; Ar = 2,6‐diisopropylphenyl), a series of test reactions was studied. Thus, treatment of 1 with Me3SiN3, (PhO)2P(O)N3, PhC(O)Ph, Me–C≡C–C≡C–Me, Ph–C≡C–C≡C–Ph, CO2, CS2, ZnCl2, or ZnEt2 yielded the respective products 9–17, all of which were characterized by elemental analyses, NMR spectroscopic investigations in the solid state and in solution, and single‐crystal X‐ray diffraction studies. The formation of compounds 9–17 is based on oxidative addition reactions (for 9–15) or Lewis acid/base reactions (for 16 and 17). In most cases, these typical silylene reactions are coupled with additional reactivity facets, which are correlated with the guanidinato or bis(trimethylsilyl)amido ligand of 1. According to these studies, silylene 1 proved to be a very useful building block with high synthetic potential for the preparation of new silicon(IV) and silicon(II) compounds, with quite novel structural motifs.
The silylene [DippNC(NMe2)NDipp]Si[N(SiMe3)2] (Dipp = 2,6‐diidopropylphenyl) proved to be a very useful building block with a high synthetic potential for the preparation of new silicon(IV) and silicon(II) compounds (see examples 1–9).