Comparison of nickel-group metal cyanides and acetylides and their anions using anion photoelectron spectroscopy and density functional theory calculations.

The photoelectron spectra of NiCN-, PdCN-, PtCN-, HNiC2H-, Ni(C2H)2(-), PdC2H-, and PtC2H- are presented along with density functional theory calculations. Linear structures are predicted for all anions and neutrals. NiCN- and NiCN are predicted to have 3delta and 2delta ground states, respectively. HNiC2H- and Ni(C2H)2(-) are predicted to have 2delta and 2delta(g) anion and 3delta and 3pi(g) neutral ground states, respectively. The palladium and platinum cyanide and acetylides have 1sigma+ anion and 2sigma+ neutral ground states. Simulations generated from the calculated parameters are compared to observed spectra, and molecular orbital diagrams are presented to compare the bonding in these species.