Organonitriles (RC equivalent to N) were selectively converted into the corresponding diborylamines (RCH2N(Bpin)(2)) in reactions with pinacolborane (pinBH) in the presence of a catalytic amount of the iron-indium complex [Fe(CH3CN)(6)] [cis-Fe(CO)(4)(InCl3)(2)]. The catalytic reaction mechanism was tentatively proposed. In addition, this catalytic system was found to be applicable for the synthesis of borylsilylamine in high yield when organonitrile was treated with hydroborane and hydrosilane simultaneously.