A base-free, catalytic protocol for the dehydrogenative Si-N coupling of weakly nucleophilic N-H groups of heteroarenes or aryl-substituted amines with equimolar amounts of hydrosilanes is reported. Cooperative Si-H bond activation at a Ru-S bond generates a silicon electrophile that forms a Si-N bond prior to the N-H deprotonation by an intermediate Ru-H complex, only releasing H(2).