Why is W(VI) more stable than Cr(VI)

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Discussion Overview

The discussion centers on the stability of Tungsten(VI) compared to Chromium(VI), exploring the reasons behind the differing reducing properties of these two elements. The conversation touches on concepts related to atomic orbitals, electron configurations, and potential repulsion effects, with a focus on theoretical and conceptual aspects.

Discussion Character

  • Exploratory, Technical explanation, Conceptual clarification, Debate/contested

Main Points Raised

  • Some participants propose that the reducing nature of Chromium(VI) compared to Tungsten(VI) may be related to the d-orbitals in Chromium being more strongly bound due to their position in the periodic table.
  • Others argue that the similarity in radius between Chromium and Tungsten does not directly account for their differing stability, suggesting that the d-orbitals' characteristics play a more significant role.
  • A participant questions whether the higher potential energy of Tungsten's orbitals is influenced by core repulsion from s-orbitals.
  • Another participant clarifies that it is the 5d orbitals in Tungsten that are relevant, not the 3d orbitals, and suggests that the repulsion involved is more accurately described as Pauli repulsion between 3d and 4d orbitals.
  • One participant requests additional resources for further reading on the topic, indicating a desire to understand the phenomena discussed, particularly regarding orbital energy and repulsion effects.

Areas of Agreement / Disagreement

The discussion contains multiple competing views regarding the reasons for the stability differences between W(VI) and Cr(VI). Participants have not reached a consensus on the underlying mechanisms or the role of orbital interactions.

Contextual Notes

Limitations include potential missing assumptions about orbital interactions and the specific definitions of stability and reducing properties. The discussion does not resolve the mathematical or theoretical steps involved in the arguments presented.

sludger13
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I'm not sure why Chromium(VI) is reducing and Tungsten(VI) isn't. I also noticed their radius is quite similar. Is that related?
 
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I think it is due to the d-orbitals in Cr being the first ones (3d) they don't have to be orthogonal to inner shells and are therefore relatively more strongly bound than 4d or 5d orbitals in the higher periods. Similar trends can be observed in the other groups, too, e.g. V vs. Nb or Ta, Fe vs Ru or Os.
 
So the (3d) orbitals in Tungsten are potentially higher? Is it due to (s) orbitals core repulsion?
 
Of course not the 3d orbitals in tungsten, but the 5d orbitals.
If you want to view this as the result of a repulsion, it is rather 3d and 4d Pauli repulsion.
 
Ok, could you place here some links... because it's better if I read something for first. The only phenomenon I'm aware of is (ns) orbital energy fall due to Pauli repulsion, and obviously this isn't the entirely same thing.
 

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