Using equilibrium isotope effects to detect intramolecular OH/OH hydrogen bonds: structural and solvent effects.
A comparative (1)H NMR study of partially deuterated 1,3- and 1,4-diols has demonstrated that intramolecular hydrogen bonds of different geometry can give rise to equilibrium isotope shifts of opposite sign in hydrogen-bond-accepting solvents such as DMSO-d(6), acetone-d(6), and THF-d(8). The sign inversion is interpreted in terms of the ability of solvent molecules to form competitive intermolecular hydrogen bonds with the diol and in terms of the limiting chemical shifts for the interior and exterior hydroxyl groups. Deuterium is shown to prefer the intermolecular solvent hydrogen bond by 10.9 +/- 0.5 cal/mol for 1,4-diol 3 dissolved in DMSO-d(6) at room temperature. Pyridine-d(5) is shown to be capable of amplifying positive (downfield) isotope shifts measured in DMSO-d(6), in some cases by as much as a factor of 3. Its use is demonstrated for the assignment of the syn or anti relative configuration of 2,4-pentanediol and for the amplification of isotope shifts used to detect intramolecular hydrogen bonds in alpha- and beta-cyclodextrin. Studies in apolar solvents such as CD(2)Cl(2) and benzene-d(6) reveal that the isotope shift is negative (upfield) for all hydrogen bond geometries studied. Larger isotope shifts are measured in benzene-d(6), and a rationale for this amplification is presented. The use of apolar solvents is particularly useful for assigning the syn or anti configuration of 2,4-pentanediol.
Vasquez
Thomas E
TE
Department of Chemistry, Pomona College, 645 North College Avenue, Claremont, CA 91711, USA.
Bergset
Jon M
JM
Fierman
Matthew B
MB
Nelson
Alshakim
A
Roth
Joshua
J
Khan
Saeed I
SI
O'Leary
Daniel J
DJ
D000438:Alcohols / Q000737:chemistry*; D003505:Cyclodextrins / Q000737:chemistry; D003903:Deuterium; D004121:Dimethyl Sulfoxide / Q000737:chemistry; D004187:Disaccharides / Q000737:chemistry; D005947:Glucose / Q000737:chemistry; D006860:Hydrogen Bonding; D007700:Kinetics; D019906:Nuclear Magnetic Resonance, Biomolecular; D011725:Pyridines / Q000737:chemistry; D012997:Solvents
D000438:Alcohols; D003505:Cyclodextrins; D004187:Disaccharides; D011725:Pyridines; D012997:Solvents; D003903:Deuterium; D005947:Glucose; C023666:pyridine; D004121:Dimethyl Sulfoxide