Abstract
C-CN bond cleavage in organonitriles was attained in the photoreaction with HSiEt3 in the presence of a catalytic amount of ( 5 -C5H5)Fe(CO)2Me. The reaction sequence was proposed, where silyl migration from Fe to N in the coordinating nitrile is a key step. DFT calculations proposed a silyl migration with small activation energy of 4.0 kcal/mol and subsequent C-CN bond cleavage on the Fe coordination sphere. N-CN bond cleavage in cyanamide (R2NCN) was also attained by a transition metal catalyst. A catalytic cycle was proposed where a silyl migration from a transition metal to the nitrile nitrogen is involved. An N-silylated 2 -amidino complex was isolated, which was shown to
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