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B(C 6 F 5 ) 3 ‐Mediated Transformations and Hydrogenation of Carbodiimides
Author(s) -
Holthausen Michael H.,
Colussi Mariah,
Stephan Douglas W.
Publication year - 2015
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.201405014
Subject(s) - carbodiimide , amidine , chemistry , isomerization , adduct , moiety , yield (engineering) , cyanamide , medicinal chemistry , reactivity (psychology) , stereochemistry , organic chemistry , catalysis , materials science , medicine , alternative medicine , pathology , metallurgy
The reactivity of a series of carbodiimides RNCNR (R= t Bu ( 1 a ), i Pr ( 1 b ), SiMe 3 ( 1 c ), and Dipp (2,6‐di‐ iso ‐propylphenyl ( 1 d )) with B(C 6 F 5 ) 3 was investigated. After initial adduct formation, several distinct reaction pathways were identified. These pathways involve either isomerization of the carbodiimide to cyanamide derivatives or insertion of a carbodiimide into a BC bond of B(C 6 F 5 ) 3 to yield four‐membered heterocycles. In the presence of dihydrogen, stepwise hydrogenation of the heteroallene moiety in the carbodiimides was achieved, which yielded the respective amidine–B(C 6 F 5 ) 3 adducts and amidinium borate salts upon reaction with one or two equivalents of H 2 , respectively.