Assignment of O-O and Mo=O Stretching Frequencies of Molybdenum/Tungsten Complexes Revisited

作者：Kee Choon Wee^*

来源：Journal of Chemistry, 2015, 2015: 439270.

DOI：10.1155/2015/439270

The assignment of peroxo stretching frequencies for Molybdenum and Tungsten complexes is studied by DFT and MP2 calculations. We found that M06 functional is unsuitable for assignment of Mo=O and O-O stretches in CpMo(eta(2) -O-2)OCH3 and we found that MP2 and even the def2-TZVP do not give accurate order of asymmetric and symmetric Mo=O stretching. We recommend the M06L, which is a good compromise between speed and accuracy, for works involving these complexes. For a series of ten Molybdenum and Tungsten complexes studied we found that, for Mo/W=O stretching frequencies at M06L/def2-TZVP, after scaling, a small RMSD of 15 cm(-1) could be obtained. However peroxo stretching frequencies RMSD remains high at 40 cm(-1) after scaling. This could potentially point out the need for reassignment of experimental peroxo frequencies in some of the works cited in this report.

• 出版日期2015
• 单位南阳理工学院