Bisisocyanide complexes of Zn(II) halides: Synthesis, structure, and application in the catalysis of isocyanides reaction with secondary amines

Coordination Chemistry of Main Group Metals with Organic Isocyanides

“…Insertion of an overcrowded silylene into hydroboranes is investigated by Kajiwara et al through the reaction of stable silylene-isocyanide complexes 26 a and 26 b with BH 3 •THF adduct. [32] The products obtained in these reactions are the first examples of stable silylborane-isocyanide complexes 27 a and 27 b (Scheme 10) characterized by IR, NMR ( 1 H, 13 C, 29 Si, and 11 B), and X-ray diffraction studies. The formation of the stable products by two possible mechanisms, as explained by Kajiwara et al, is outlined in Scheme 11.…”

“…[61] The proposed mechanism leading to the formation of these products is depicted in Scheme 50. Both the products were well characterized by 1 H, 13 C, 29 Si NMR spectroscopy, and single-crystal Xray diffraction studies. The activation of XylNC by electrophilic σ-silane compounds 126a, 126 b present in Ru(II) complexes to form Fischer carbene complexes are described by Lipke and Tilley.…”

“…of isocyanide also yielded silacyclopropyl anion 142 through the CÀ C coupling reaction (Scheme 55b). The structures of all the products obtained in Scheme 55 are well characterized through 29 Si NMR spectroscopy and singlecrystal X-ray analysis.…”

“…[69] However, the reaction occurred via the formation of intermediate 149, which is evident from 1 H NMR spectral analysis (Scheme 58). Intermediate 149 was highly reactive to isolate, so the authors performed the reaction under a CO atmosphere and isolated the compound 151, followed by treatment with CyNC, leading to compound 152 characterized by 1 H, 13 C, and 29 Si NMR spectroscopy, and single-crystal X-ray diffraction analyses.…”

Zinc(ii)-mediated diastereoselective Passerini reactions of biocatalytically desymmetrised renewable inputs

“…We believe that the formation of a complex such as 12 might represent the first step, which a recent report that ZnBr 2 could even form a complex with two isocyanides lends support to. 45 There could be an equilibrium between 12 and ZnBr 2 (CN-R) 2 , together with an exchange process with acetic acid that can lead to monoacetate 13, which may be the real reacting species. With this backdrop, the chelated transition state I, which we initially hypothesized, would favour the syn product due to the steric encumbrance of the lower carbonyl face.…”