Boron-11 and fluorine-19 nuclear magnetic resonance pairwise interaction parameters. Application to donor-acceptor interactions in boron trihalide adducts

1974 ◽  
Vol 13 (6) ◽  
pp. 1467-1471 ◽  
Author(s):  
J. Stephen. Hartman ◽  
Jack M. Miller
Keyword(s):  
Nuclear Magnetic Resonance ◽  
Magnetic Resonance ◽  
Pairwise Interaction ◽  
Interaction Parameters ◽  
Donor Acceptor ◽  
Nuclear Magnetic

Nuclear magnetic resonance studies of ketone•BF3 complexes. II. The boron trifluoride catalyzed condensation of acetone

1968 ◽  
Vol 46 (24) ◽  
pp. 3799-3811 ◽  
Author(s):  
R. J. Gillespie ◽  
J. S. Hartman
Keyword(s):  
Nuclear Magnetic Resonance ◽  
Magnetic Resonance ◽  
Boron Trifluoride ◽  
Methylene Chloride ◽  
Aldol Condensation ◽  
Condensation Reaction ◽  
Magnetic Resonance Studies ◽  
Exchange Processes ◽  
Donor Acceptor ◽  
Nuclear Magnetic

A detailed study of the reactions of the acetone•BF3 complex in excess acetone has been carried out by "F nuclear magnetic resonance (n.m.r.) spectroscopy. It is shown that rapid reversible fluorine exchange processes occur in solution, in addition to the slower aldol condensation–dehydration reaction. Two of the new 19F absorptions which appear during the reaction are shown to arise from BF3 complexes of donors which are formed by condensation and dehydration of acetone. The rate of the aldol condensation reaction is shown to fall off markedly as an increasing proportion of the BF3 becomes complexed with water; thus BF3 catalysis of the reaction appears to depend on the existence of a ketone–BF3 donor–acceptor bond. 1H and 19F n.m.r. studies of the acetone•BF3 complex in methylene chloride throw some light on the apparent greatly decreased reactivity of the complex in this solvent. Evidence is presented for the reversibility of the first step of the condensation reaction.

A 19F Nuclear Magnetic Resonance Study of Halogen Exchange between Antimony Pentafluoride and Inorganic Chlorides. Complexes of Antimony and Arsenic Pentafluorides with Carbonyl Fluoride

1971 ◽  
Vol 49 (8) ◽  
pp. 1276-1283 ◽  
Author(s):  
J. Bacon ◽  
P. A. W. Dean ◽  
R. J. Gillespie
Keyword(s):  
Nuclear Magnetic Resonance ◽  
Magnetic Resonance ◽  
Low Temperatures ◽  
Nuclear Magnetic Resonance Study ◽  
Antimony Pentafluoride ◽  
Magnetic Resonance Study ◽  
Halogen Exchange ◽  
Donor Acceptor ◽  
Carbonyl Fluoride ◽  
Nuclear Magnetic

19F nuclear magnetic resonance (n.m.r.) has been used to study the reactions occurring in the systems SbCl5–SbF5–SO2ClF, SO2Cl2–SbF5–SO2ClF, COF2–SbF5–SO2ClF, COF2–AsF5–SO2ClF, and COClF–SbF5–SO2ClF. Ionization occurs in SbCl5–SbF5–SO2ClF, yielding antimony chloro- and chloro-fluorocations and antimony polyfluoroanions. Donor-acceptor complexes are formed between SbF5 and SO2Cl2, COF2 or COClF at low temperatures and also between AsF5 and COF2. In all the complexes the ligand is oxygen-bonded. At higher temperatures halogen exchange and ionization occurs in SO2Cl2–SbF5–SO2ClF and COClF–SbF5–SO2ClF giving SO2ClF and COF2 complexes, respectively, together with antimony cations and polyfluoroanions. The alkyl chloride –SbF5 reaction is also shown to give chlorine-containing cations of antimony.

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