Coordinate Covalent C → B Bonding in Phenylborates and Latent Formation of Phenyl Anions from Phenylboronic Acid

Abstract

The results are reported of a theoretical study of the addition of small nucleophiles Nu- (HO- , F-) to phenylboronic acid Ph - B(OH)2 and of the stability of the resulting complexes [Ph - B(OH)2Nu]- with regard to Ph - B heterolysis [Ph - B(OH)2Nu]- → Ph- + B(OH)2Nu as well as Nu-/Ph- substitution [Ph - B(OH) 2Nu]- + Nu- → Ph- + [B(OH)2Nu2]-. These reactions are of fundamental importance for the Suzuki - Miyaura cross-coupling reaction and many other processes in chemistry and biology that involve phenylboronic acids. The species were characterized by potential energy surface analysis (B3LYP/6-31+G*), examined by electronic structure analysis (B3LYP/6-311++G**), and reaction energies (CCSD/6-311++G**) and solvation energies (PCM and IPCM, B3LYP/6-311++G**) were determined. It is shown that Ph - B bonding in [Ph - B(OH)2Nu]- is coordinate covalent and rather weak ( < 50 kcal·mol-1). The coordinate covalent bonding is large enough to inhibit unimolecular dissociation and bimolecular nucleophile-assisted phenyl anion liberation is slowed greatly by the negative charge on the borate's periphery. The latter is the major reason for the extraordinary differences in the kinetic stabilities of diazonium ions and borates in nucleophilic substitution reactions despite their rather similar coordinate covalent bond strengths.

Department(s)

Chemistry

Keywords and Phrases

Dissociation; Electronic Structure; Inorganic Acids; Molecular Structure; Negative Ions; Potential Energy; Rate Constants; Diazonium Ions; Phenyl Anions; Phenylboronic Acid; Phenolic Resins

International Standard Serial Number (ISSN)

1089-5639; 1520-5215

Document Type

Article - Journal

Document Version

Citation

File Type

text

Language(s)

English

Rights

© 2006 American Chemical Society (ACS), All rights reserved.

Publication Date

01 Feb 2006

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