An aminopyridinato ligand stabilized and coordinatively unsaturated dimeric tungsten(0) complex having an electronic structure with six metal centred HOMOs (σ2,π2,π2,δ2,δ2, and δ*2) has been isolated and structurally characterized. Its reaction with a cryptand leads to a C-H bond activation of one of the isopropyl groups of the N-ligand to form a dimeric tungsten(i) complex.