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| Content Provider | Royal Society of Chemistry (RSC) |
|---|---|
| Author | Farrimond, M. S. Allen, G. C. Clack, D. W. |
| Copyright Year | 1971 |
| Abstract | MO calculations using the complete neglect of differential overlap approximation are made for the octahedral hexafluorometallate(III) and the relatively high-oxidation-state hexafluorometallate(IV) complex ions of the firsttransition series. For these latter complex ions the ordering of the ‘metal’ orbitals is consistent with ligand-field theory when the calculations are performed using internuclear distances which are close to those observed experimentally. A variation in this parameter produces a movement of the ‘d’ occupied orbitals into the bonding set of molecular orbitals. Comparison with experimental data and with previous calculations shows that the changes in internuclear separation and derived quantities such as covalency incurred from MF64– through MF63– to MF62– are always calculated to be in the right direction (increase in covalency and decrease in internuclear separation) and in general to be of the right magnitude. Distorted configurations are found for those ions which have orbitally degenerate electronic ground-states in accordance with Jahn–Teller predictions. However, the successive removal of electrons (for the process MII→ MIII→ MIV) from orbitals which are essentially ‘metal d’ in character places some restrictions on the method when it is used for calculations on octahedral complexes containing metals in high oxidation states. |
| Starting Page | 2728 |
| Ending Page | 2733 |
| Page Count | 6 |
| File Format | |
| ISSN | 00224944 |
| Volume Number | 0 |
| Journal | Journal of the Chemical Society A: Inorganic, Physical, Theoretical |
| DOI | 10.1039/J19710002728 |
| Language | English |
| Publisher | Royal Society of Chemistry |
| Access Restriction | Open |
| Subject Keyword | Jahn Jahn\u2013Teller effect |
| Content Type | Text |
| Resource Type | Article |
| Subject | Physical and Theoretical Chemistry Inorganic Chemistry |
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