Experimental and theoretical evidence for the formation of zinc tricarbonyl in solid argon

Zinc carbonyls are extremely rare. Here we report experimental and theoretical evidence of unprecedented zinc tricarbonyl, Zn(CO)3, the next member of the series of 18-electron metal carbonyls Cr(CO)6 --> Fe(CO)5 --> Ni(CO)4, whereas there is no evidence for the formation of the zinc mono- and dicarbonyls Zn(CO)n (n = 1, 2). DFT calculations predict that the Zn(CO)3 molecule has a singlet ground state with D3h symmetry. The formation of Zn(CO)3 involves 4s --> 4p promotion of the Zn atom, which increases the Zn-CO bonding by decreasing the sigma repulsion and significantly increasing the Zn 4sp hybrid orbitals --> CO pi* back-donation.