A novel PNP-pincer type phosphaalkene complex of iridium bearing a dearomatized pyridine unit (3) has been prepared. Complex 3 rapidly reacts with ammonia at room temperature to afford a parent amido complex in high yield. DFT calculations indicate that the phosphaalkene unit with a strong pi-accepting property effectively facilitates the N-H bond cleavage of ammonia via metal-ligand cooperation.