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The carbonyl resonance in 13C NMR spectrum of [(η5-C5H5)Rh(CO)]3, (103Rh, nuclear spin, I= 1/2, 100%) shows a triplet at –65º C owing to the presence of
- a)Terminal CO
- b)μ2-CO
- c)μ3-CO
- d)η5 - C5H5
Correct answer is option 'B'. Can you explain this answer?
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Most Upvoted Answer
The carbonyl resonance in13C NMR spectrum of [(η5-C5H5)Rh(CO)]3, (...
Explanation:
μ2-CO:
- The triplet at -65°C in the 13C NMR spectrum of [(η5-C5H5)Rh(CO)]3 is due to the presence of μ2-CO.
- The μ2-CO ligand is bridging between two Rhodium atoms, resulting in a unique chemical environment for the carbon atom in the carbonyl group.
- This leads to a distinct resonance in the 13C NMR spectrum, giving rise to the observed triplet.
Terminal CO:
- If the triplet was due to a terminal CO ligand, it would show different chemical shifts in the NMR spectrum compared to a μ2-CO ligand.
- Terminal CO ligands typically have different chemical environments and would not produce a triplet at -65°C in the 13C NMR spectrum.
μ3-CO:
- The presence of a μ3-CO ligand would also result in a different chemical environment for the carbon atom in the carbonyl group.
- This would lead to a different resonance pattern in the NMR spectrum compared to the observed triplet at -65°C.
η5-C5H5:
- The η5-C5H5 ligand is not directly responsible for the triplet at -65°C in the 13C NMR spectrum.
- While it contributes to the overall chemical environment of the complex, it does not cause the specific resonance observed for the carbonyl group.
μ2-CO:
- The triplet at -65°C in the 13C NMR spectrum of [(η5-C5H5)Rh(CO)]3 is due to the presence of μ2-CO.
- The μ2-CO ligand is bridging between two Rhodium atoms, resulting in a unique chemical environment for the carbon atom in the carbonyl group.
- This leads to a distinct resonance in the 13C NMR spectrum, giving rise to the observed triplet.
Terminal CO:
- If the triplet was due to a terminal CO ligand, it would show different chemical shifts in the NMR spectrum compared to a μ2-CO ligand.
- Terminal CO ligands typically have different chemical environments and would not produce a triplet at -65°C in the 13C NMR spectrum.
μ3-CO:
- The presence of a μ3-CO ligand would also result in a different chemical environment for the carbon atom in the carbonyl group.
- This would lead to a different resonance pattern in the NMR spectrum compared to the observed triplet at -65°C.
η5-C5H5:
- The η5-C5H5 ligand is not directly responsible for the triplet at -65°C in the 13C NMR spectrum.
- While it contributes to the overall chemical environment of the complex, it does not cause the specific resonance observed for the carbonyl group.
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The carbonyl resonance in13C NMR spectrum of [(η5-C5H5)Rh(CO)]3, (...
- To discuss the appearance of a triplet in the 13C NMR of a rhodium complex like [(-C5H5)Rh(CO)]3, we need to clarify which nuclei are splitting the carbonyl carbon signal.
- In this case, the carbonyl carbon atom of the CO ligand in each Rhodium complex is surrounded by two other equivalent carbonyl carbon atoms within this trimer structure. The combined influence of those two equivalent carbonyl carbon atoms results in a triplet for the carbonyl carbon in the 13C NMR spectrum.
- An important note here is that the splitting is observable because Rhodium 103 isotope, which is the only naturally occurring rhodium isotope, has a nuclear spin value (I) of 1/2 (i.e., it's NMR active).
- Thus, it facilitates indirect coupling if it's involved in the through-space spin transfer (known as J coupling) between the carbonyl carbons. These spin couplings are generally not through-bond interactions like typical NMR coupling
- So, the carbonyl resonance in 13C NMR spectrum of [(η5-C5H5)Rh(CO)]3, (103Rh, nuclear spin, I= 1/2, 100%) shows a triplet at –65º C owing to the presence of μ2-CO
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The carbonyl resonance in13C NMR spectrum of [(η5-C5H5)Rh(CO)]3, (103Rh, nuclear spin, I= 1/2, 100%) shows a triplet at –65º C owing to the presence ofa)Terminal COb)μ2-COc)μ3-COd)η5- C5H5Correct answer is option 'B'. Can you explain this answer?
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