This work describes a new atom-economical catalytic process for the guanylation of amines with a broad substrate scope using the half-sandwich titanacarborane amide [ sigma: eta(1): eta(5)-( OCH2)( Me2NCH2)( C2B9H9)] Ti( NMe2) as catalyst. This species bears two different sidearms: one is strongly bonded to the Ti center by taking the advantage of its high oxophilicity, whereas the other is hemilabile in nature, binding the Ti center reversibly.
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