Chemistry Complex ion oxidation state (with pic)

AI Thread Summary
The oxidation state of central cobalt in the discussed complex is debated, with one participant suggesting it is +6 due to surrounding oxygen, while another argues that oxidation states are merely accounting tools without real measurable properties. Assigning oxidation states in large complexes is seen as unhelpful since these atoms are part of a molecular structure bonded through molecular orbitals. The discussion highlights the importance of charge density measurements over arbitrary oxidation state assignments. There is also a correction regarding the presence of hydroxide ions that balance the charge in the complex. Ultimately, the conversation underscores the complexity of oxidation states in coordination chemistry and their practical implications for understanding chemical behavior.
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Homework Statement
What are the oxidation states of the cobalt ions?
Relevant Equations
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question fig:
圖片1.png

solution manual:
圖片2.png

my solution:
oxidation state of central cobalt is +6 due to 6 oxygen surrounding it,The other cobalt is +2 due to 2 oxygen surrounding it with NH3 ligand which is no count for oxidation state.
 
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First of all, please remember oxidation state doesn't exist - it is merely an accounting device helping in electron bookkeeping, in most cases there is no measurable property of an atom that can be measured and called "oxidation state".

Then, assigning oxidation states to atoms in large complexes doesn't make much sense. They don't exist in separation but are all part of molecule and are bonded with molecular orbitals. Using arbitrary rules to assign some number to an atom doesn't produce any real insight into what is really happening. We can measure charge density with some spectroscopic methods, but it will show electron cloud that can't be easily split into "charges on atoms".
 
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On the other hand...

Let us evaluate your answer. You say that the central Co is +6 and each of the three “ligand” Co complexes contains a Co+2. This gives a total charge of 6+2+2+2=+12. This total charge is balanced by only 6 Cl-1?
 
I agree with Borek as a theoretical chemist, but from practical chemistry side, there are many examples where oxidation state is useful beyond electron counting. E.g. there are compounds like Fe3O4 where the iron ions are in differently coordinated sites and also differ in their spectroscopic behaviour so that the compound is better regarded as an Fe(II) Fe(III)2 O4 than a Fe(2.66)3O4.
 
Borek said:
@chemisttree I feel like you may have missed 6 OH-?
You’re right, I did miss the the 6 OH-1. 😐
 
Borek said:
First of all, please remember oxidation state doesn't exist - it is merely an accounting device helping in electron bookkeeping, in most cases there is no measurable property of an atom that can be measured and called "oxidation state".

Then, assigning oxidation states to atoms in large complexes doesn't make much sense. They don't exist in separation but are all part of molecule and are bonded with molecular orbitals. Using arbitrary rules to assign some number to an atom doesn't produce any real insight into what is really happening. We can measure charge density with some spectroscopic methods, but it will show electron cloud that can't be easily split into "charges on atoms".
According to textbook, what you said is true but I still have to tackle the exam...please educate me why its oxidation number is 3 for all cobalts
 
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You would have to know that Co+6 is not a known oxidation state of cobalt. That unknown ion (maybe you will find it in the sun’s coronasphere) would be isoelectronic with scandium. [Ar]4s23d1 would be pretty unusual for Co, right? And try to add six pairs of electrons to that and see if it looks right to you?
 
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