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C ‐Silyl‐ N , N ‐dialkyl‐ N′ ‐arylformamidines: Synthesis and Reactions with Phosphorus(III) Chlorides
Author(s) -
Marchenko Anatoliy,
Koidan Georgyi,
Hurieva Anastasiya,
Vlasenko Yurii,
Kostyuk Aleksandr
Publication year - 2016
Publication title -
european journal of inorganic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.667
H-Index - 136
eISSN - 1099-0682
pISSN - 1434-1948
DOI - 10.1002/ejic.201600803
Subject(s) - chemistry , silylation , trimethylsilyl , steric effects , phosphorus trichloride , deprotonation , medicinal chemistry , phosphorus , tris , organic chemistry , catalysis , ion , biochemistry
A method for the synthesis of new C ‐silyl‐ N , N ‐dialkyl‐ N′ ‐arylformamidines was developed. These derivatives were formed by the deprotonation of N ‐(trimethylsilyl)formamidinium salts to give the corresponding N ‐trimethylsilyl carbenes followed by a 1,2‐migration of the silyl group. The reactions of C ‐silylformamidines with phosphorus(III) chlorides were then studied. The reactions between chlorodiphenylphosphane and the C ‐silylformamidines readily afforded C ‐phosphanylformamidines in high yields. The reactions of dichlorophosphanes and C ‐silylformamidines yielded previously unknown phosphanes that feature two formamidine substituents. In the reaction with phosphorus trichloride, the sterically least encumbered formamidine gave a stable two‐coordinate compound through the formation of an intermediate tris(phosphane). The reactions of the sterically more encumbered formamidines led to the substitution of only two chlorine atoms to give a chlorophosphane or benzazaphosphole. The structures of key compounds were proven by X‐ray crystal structure analyses.