Friday, October 25, 2019

11B Double Quantum - Single Quantum Correlation Spectroscopy

The 2D 13C INADEQUATE method provides double quantum - single quantum (DQ/SQ) correlations and enables one to determine the carbon - carbon skeleton of small organic molecules.  The method is quite insensitive for 13C since the natural abundance of 13C is only 1.1% and the chance of having two adjacent 13C nuclei is only 1 in 8264.  For spins other than 13C, for which the natural abundance is high, one expects the sensitivity of DQ/SQ correlation spectroscopy to be much higher.  11B has a natural abundance of 80.42% and the chance of having two adjacent 11B nuclei in compounds with boron-boron bonds is 1 in 1.55.  11B NMR spectra are often sufficiently broad due to efficient quadrupolar relaxation such that homonuclear 11B - 11B J coupling is unresolved however the T2's are long enough to allow the collection of  2D 11 B COSY and 2D DQ/SQ data.  The figure below shows the 2D 11B DQ/SQ correlation spectrum of ortho-carborane.  The 11B bonding connectivity can be determined easily from the spectrum.

7 comments:

~H2O+ said...

Dear Glenn,

Which pulse program for bruker NMR should be used to perform this experiment?

How long will be the experimental time?

Thank you so much!

H2O

Glenn Facey said...

H2O,
These data were collected on a Bruker AVANCE IIIHD 500 using the inadqf pulse sequence. NS=32, DS=16, D1=1sec, 64 slices. The spectrum took about 40 minutes to acquire.
Glenn

~H2O+ said...

Dear Glenn,

Thank you so much!

So for relatively abundant nucleus like 11B, 2D INADEQUATE and COSY deliver the same structural information? But in terms of experimental time, COSY seems better than INADEQUATE.

H2O

Glenn Facey said...

H2O,
Yes COSY and INADEQUATE can provide similar information.
Glenn

Eugene said...

These posts are great! Thanks for posting!

John Stew said...

Hi Glenn,

Have you tried to run a DQ-SQ on a quadrupolar nuclei (ssnmr)? I want to probe proximities of Boron sites on glass. I´m trying to find such pulse program online but with no luck. Maybe you can help me with that

Glenn Facey said...

John,
I have no experience with DQ-SQ 2D spectra of 11B in solid samples but you may get some more information from this reference:

https://pubs.rsc.org/en/content/articlelanding/2017/cp/c6cp06555d#!divAbstract

Glenn