Addition of Lappert%26apos;s Stannylenes to Carbodiimides, Providing a New Class of Tin(II) Guanidinates

作者：Chlupaty Tomas; Padelkova Zdenka; DeProft Frank; Willem Rudolph; Ruzicka Ales^*

来源：Organometallics, 2012, 31(6): 2203-2211.

DOI：10.1021/om201118m

Reactions of bis[bis(trimethylsilyl)amino]tin and the dimer of [bis(trimethylsilyl)amino]tin chloride with various carbodiimides give pure corresponding tin(II) guanidinates in essentially quantitative yields. Heteroleptic bis(trimethylsilyl)amido ({R-NC[N-(SiMe3)(2)]N-R}SnN(SiMe3)(2))- and chloro-substituted ({R-NC}[N-(SiMe3)(2)]N-R}SnCl) tin(II) guanidinates were obtained from reactions of N,N%26apos;-diisopropyl-, N,N%26apos;-dicyclohexyl-, N,N%26apos;-bis(4-methylphenyl)-, and N-[3-(dimethylamino)propyl]-N%26apos;-ethylcarbodiimides, respectively. Homoleptic tin(II) guanidinates {R-NC[N(SiMe3)(2)]N-R}(2)Sn were obtained from the N,N%26apos;-bis(4-methylphenyl)- and N-[3-(dimethylamino)propyl]-N%26apos;-ethyl-substituted carbodiimides. Similar reactions of N,N%26apos;-bis(2,6-diisopropylphenyl)- and N,N%26apos;-bis(trimethylsilyl)carbodiimide, respectively, having the bulkiest substituents of the series, failed to take place under various conditions. The complexes prepared were characterized as monomers in solution by H-1, C-13, and Sn-119 NMR spectroscopy in C6D6 and THF-d(8). The solid-state NMR spectra were recorded for structure comparison. X-ray diffraction studies of one homoleptic monomer, two heteroleptic chloro complexes with the structures of two different types of dimers, and the oxidation product of the heteroleptic bis(trimethylsilyl)amido-substituted guanidinate-a centrosymmetric (guanidinato)tin(IV) oxide-were performed on appropriate crystals. Attempts to prepare homoleptic types of isopropyl- and cyclohexyl-substituted tin(II) guanidinate complexes were unsuccessful. The structures were also evaluated by DFT methods.

• 出版日期2012-3-26