A density functional study on the geometries and bond dissociation energies of Mo(CO)(n)(+) (n = 1 similar to 6) compounds

作者：Zhang YF^*; Xiang SC; Li JQ

来源：Acta Chimica Sinica, 2000, 58(8): 962-970.

• Mo(CO)(n)(+) (n=1 similar to 6) compounds
• density functional method
• natural bond orbital
• bond dissociation energy

The ground geometries of Mo(CO)(n)(+) (n = 1 similar to 6) compounds were studied by using DFT/B3LYP method. The structure and ground state of each fragment ion are C-infinity v((6)Sigma(+)), D-infinity h((6)Sigma(g)(+)), C-2v((2)A(2)) or D-3h((6)A(1)), D-4h((4)A(1g)), C-2v(B-2(2)) or C-4v(t)(B-2(1)), and D-3d((2)A(1g)) for n = 6 sequentially. The results indicate that the geometry of each species (n greater than or equal to 3) is sensitive to the spin state. The sequential bond dissociation energies (D-0) for CO-Mo(CO)(n-1)(+) are also calculated, and the results are in good agreement with the experiment, while the D-0 for n = 3 is too small. The D-0 values varied nonmonotonically with the number of ligands were discussed in term of 5s4d hybridization of Mo atom. In addition, the relations between the number of CO and the stability of fragment ions were discussed by analyzing the spin multiplicities of the system.

• 出版日期2000
• 单位福州大学