# Correlation between 1H and 13C shifts - coincidence or not?

A quick glance at any table of typical chemical shifts will reveal that the chemical shifts of protons $(\delta_\mathrm H)$ tend to correlate pretty well with the chemical shifts of the carbons to which they are attached $(\delta_\mathrm C)$. This correlation is frequently taught in introductory organic chemistry and the rule of thumb

$$\delta_\mathrm C \approx 20 \cdot \delta_\mathrm H,$$

although simplistic, actually holds up fairly well. To illustrate the point further, here is a diagram taken from the textbook by Silverstein et al. on organic spectroscopy:

Image taken from: Silverstein, R. M.; Webster, F. X.; Kiemle, D. J. Spectrometric Identification of Organic Compounds, 7th ed.; Wiley: Hoboken, NJ, 2005, p 207.

To the beginner such a correlation might seem intuitive. However, delving deeper into NMR theory, one learns that the $\ce{^{13}C}$ chemical shifts are generally dictated by paramagnetic shielding, while $\ce{^{1}H}$ chemical shifts are generally dictated by diamagnetic shielding and effects due to neighbouring groups. See, for example, this question: NMR chemical shift range of different elements.

In light of this, how much should we make out of the general correlation seen? i.e., is it best understood to be a pure coincidence, or is there more to it than that?

• I've never actually been taught that rule of thumb regarding dH shifts and dC shifts. Learnt something new today. THANKS! – Hazinga Aug 10 '17 at 20:36
• I don't have the understanding to actually answer, but the conclusion has been drawn before and was definitely pointed out during my undergrad tutorials. Seems to be a coincidence that holds up okay for simple things. See J. Chem. Educ. 1991, 68, 284. An old article, with no explanation, but does offer an empirical conversion based on a training set of 53 (complex-ish) molecules. – NotEvans. Aug 19 '17 at 18:04