Ammonia is a central vector in sustainable global growth, but the usage of fossil feedstocks and centralized Haber-Bosch synthesis conditions causes >1.4% of global anthropogenic CO 2 emissions. While nitrogenase enzymes convert atmospheric N 2 to ammonia at ambient conditions, even the most active manmade inorganic catalysts fail due to low activity and parasitic hydrogen evolution at low temperatures. Here, we show that the [RuH 6 ] catalytic center in ternary ruthenium complex hydrides (Li 4 RuH 6 ) activates N 2 preferentially and avoids hydrogen over-saturation at low temperatures and near ambient pressure by delicately balancing H 2 chemisorption and N 2 activation. The active [RuH 6 ] catalytic center is capable of achieving high yield at low temperatures via a shift in the rate-determining reaction intermediates and transition states, where the reaction orders in hydrogen and ammonia change dramatically. Temperature-dependent atomic-scale understanding of this unique mechanism is obtained with synchronized experimental and density functional theory investigations. • Atomic-scale study reveals how Li 4 RuH 6 catalyzes NH 3 at a low temperature • Li 4 RuH 6 inherently balances N 2 activation/H 2 chemisorption to avoid H poisoning • The reaction orders of hydrogen and ammonia change with a temperature change The NH 3 industry is energy intensive, fossil-fuel based, responsible for >2% of the world’s CO 2 emission, and awaits a green technology. Pan et al. study how Li 4 RuH 6 activates N 2 , preferentially avoids H poisoning, and produces NH 3 at low temperatures, potentially informing greener NH 3 synthesis design.