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- W4205802014 abstract "Abstract Point‐charge crystal field theory (CFT) for linear ML 2 systems guarantees d z 2>d xz /d yz >d xy /d x 2 ‐y 2 (i. e. dσ>dπ>dδ). This is not what is found for CuCl 2 and other linear, divalent MX 2 complexes where dπ>dσ. This failure of CFT has also been attributed to its successor, ligand field theory (LFT). However, taking LFT to be parameterised CFT, any d orbital sequence is possible. The real test is whether the LFT parameters make chemical sense. A new cellular ligand field (CLF) analysis of CuCl 2 , including the equatorial toroidal void, which affects all the d orbitals, confirms e π (Cl)>e σ (Cl). To account for this, the ‘distributed donation’ model is proposed linking σ and π bonding such that enhanced π donation is at the expense of reduced σ bonding and vice versa. This is the π‐donor analogue of the Dewar‐Chatt‐Duncanson model for π‐acceptor ligands. Ab initio LFT (AI LFT) calculations support a progressive π‐donation increase/σ donation decrease from Cu(II) to Sc(II) with e σ finally becoming negative. The model further predicts that adding equatorial ligands will force the π density back into the σ bond which is also confirmed by AI LFT calculations for trans‐ [CuCl 2 (NH 3 ) 4 ] where e σ (Cl)>e π (Cl) even though the CuCl 2 unit is unchanged. The distributed donation model for linear σ‐only [M II (L σ ) 2 ] n systems (L σ =NH 3 , H), where increasing π donation is not possible, implies that the M−L bonding in linear systems should be inherently weak." @default.
- W4205802014 created "2022-01-25" @default.
- W4205802014 creator A5018390138 @default.
- W4205802014 date "2021-12-30" @default.
- W4205802014 modified "2023-10-04" @default.
- W4205802014 title "Ligand Field Theory for Linear ML 2 Complexes" @default.
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- W4205802014 doi "https://doi.org/10.1002/ejic.202100936" @default.
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