TY - JOUR

T1 - Dess-martin periodinane

T2 - The reactivity of a λ5-iodane catalyst explained by topological analysis

AU - Tantardini, Christian

AU - Michalchuk, Adam A.L.

N1 - Publisher Copyright: © 2018 Wiley Periodicals, Inc.

PY - 2019/3/15

Y1 - 2019/3/15

N2 - Dess-Martin periodinane (DMP) and its derivatives are popular organic catalysts. DMP is extremely reactive in the presence of alcohols, catalyzing their oxidative conversion into ketones. However, despite their widespread use, this reactivity has not yet been explained. In the present work, a quantum chemical topological approach is taken to study the electronic structure of DMP. Topological analysis revealed two of the Iodine interpuncts ligand interactions to be notably weaker than the two others. Combined with study of the domain-averaged Fermi hole (DAFH), it was confirmed that the iodine center is λ 5 -hypervalent, forming two 3-center-4-electron and two 3-center-2-electrons bonds. The weakness of these multicenter bonds is ascribed to the high reactivity displayed by DMP. The ability to tune the ligand-iodine interactions is investigated by altering the electronic structure of the ligands. It is demonstrated that DAFH analysis offers powerful insight into the understanding of molecular reactivity.

AB - Dess-Martin periodinane (DMP) and its derivatives are popular organic catalysts. DMP is extremely reactive in the presence of alcohols, catalyzing their oxidative conversion into ketones. However, despite their widespread use, this reactivity has not yet been explained. In the present work, a quantum chemical topological approach is taken to study the electronic structure of DMP. Topological analysis revealed two of the Iodine interpuncts ligand interactions to be notably weaker than the two others. Combined with study of the domain-averaged Fermi hole (DAFH), it was confirmed that the iodine center is λ 5 -hypervalent, forming two 3-center-4-electron and two 3-center-2-electrons bonds. The weakness of these multicenter bonds is ascribed to the high reactivity displayed by DMP. The ability to tune the ligand-iodine interactions is investigated by altering the electronic structure of the ligands. It is demonstrated that DAFH analysis offers powerful insight into the understanding of molecular reactivity.

KW - dess-martinperiodinane (DMP)

KW - domain-averaged-Fermi-hole (DAFH)

KW - Espinosa-indexes

KW - quantum-theory-atom-inmolecules (QTAIM)

KW - source function (SF)

KW - Dess-Martin periodinane (DMP)

KW - quantum-theory-atom-in-molecules (QTAIM)

KW - ORGANIC-SYNTHESIS

KW - ORGANOMETALLIC COMPOUNDS

KW - MOLECULAR-ORBITAL METHODS

KW - GAUSSIAN-TYPE BASIS

KW - IODINE(V) REAGENTS

KW - SECONDARY ALCOHOLS

KW - O-IODOXYBENZOIC ACID

KW - VALENCE BASIS-SETS

KW - EXTENDED BASIS-SETS

KW - AVERAGED FERMI HOLES

UR - http://www.scopus.com/inward/record.url?scp=85057294975&partnerID=8YFLogxK

U2 - 10.1002/qua.25838

DO - 10.1002/qua.25838

M3 - Article

AN - SCOPUS:85057294975

VL - 119

JO - International Journal of Quantum Chemistry

JF - International Journal of Quantum Chemistry

SN - 0020-7608

IS - 6

M1 - 25838

ER -