Insights into the Metal-CO Bond in O 2 M(η 1 -CO) (M = Cr, Mo, W, Nd, and U) Complexes.

Investigations on the structures and bonding properties of metal carbonyl compounds provide fundamental understandings on the origin of small-molecule activations. Herein, the geometry and bonding trends of a series of isovalent metal oxocarbonyl complexes O 2 M(η 1 -CO) (M = Cr, Mo, W, Nd, and U) were studied by combined matrix-isolation infrared spectroscopy and advanced quantum chemical calculations. The title complexes present red shift of C-O stretching bands in the range from 122 to 244 cm -1 , indicating the difference of CO activation ability for the series of isovalent metal dioxides. Density functional theory calculations predict T-shaped structures with a C 2v symmetry for all the title molecules. O 2 Nd(η 1 -CO) bears little resemblance to the other complexes in bonding characters because of the weak interactions between the NdO 2 and CO moiety. For the other complexes, natural localized molecular orbital analysis reveals a gradual increase of covalent character in M-CO bonds along the metal series Cr → Mo → W→ U. Energy decomposition analysis with natural orbitals for chemical valence calculations demonstrates that the M-CO bonding patterns conform to the conventional Dewar-Chatt-Duncanson motif. The contributions from orbital interactions in total attractions increase from Cr (41.7%) to U (52.7%). The breakdown of the orbital term into pairwise interactions shows that contributions of the M ← CO σ donation decrease from Cr (59.2%) to U (28.4%), while the M → CO π* backdonation increases significantly from Cr (23.8%) to U (67.3%). The more effective overlap and the better energy matching of U 5f and U 6d valence orbitals with CO π* orbitals result in much stronger U → CO π backdonation than the other metal elements.