An ab initio and MNDO-d SCF-MO Computational Study of Stereoelectronic Control in Extrusion Reactions of R2I-F Iodine (III) Intermediates.

Michael A. Carroll, Sonsoles Martin-Santamari, Victor W. Pike, Henry S. Rzepa* and David A. Widdowson

Department of Chemistry, Imperial College of Science, Technology and Medicine, London, SW7 2AY, UK; Chemistry and Engineering Group, MRC Cyclotron Unit, Imperial College School of Medicine, Hammersmith Hospital, Ducane Road, London, W12 0HS UK.

Supplemental Information

Table 1. Energies, Hartree (activation barriers, kcal mol-1) and transition normal mode (cm-1) for the stationary point structures R=RŐ=H.

Table 2. Energies, (activation barriers, kcal mol-1) and transition wavenumber (cm-1) for stationary point structures (RHF/3-21G(d)/Hartree, B3LYP/3-21G(d)/Hartree, MNDOD/kcal mol-1).

Table 3. Energies (activation barriers, kcal mol-1) and first normal mode (cm-1) for the stationary point structures (RHF/3-21G(d)/Hartree, B3LYP/3-21G(d)/Hartree, MNDOD/kcal mol-1).

Table 5. Energies (dimerisation/activation) and first normal mode (cm-1) for stationary point structures (RHF/3-21G(d)/Hartree, B3LYP/3-21G(d)/Hartree, B3LYP/DZVP/Hartree, MNDOD/kcal mol-1).

Structures of R2I-X Systems (X=Cl...I)

R2I-Cl symmetric dimerR2I--Br symmetric dimer
R2I-Br, dimer + tetramerR2I-I symmetric dimer

Structures of R2I-O Systems

R2I...NO2 as pseudo dimerR2I..OTf as pseudo dimer
R2I...OTs as dimerR2I...O as trimer

Structures of R2Br and Cl Systems

Ph2Br-IPh2Br-Br
RR'Br...OTfRR'Cl...SbCl6

Structures of RIZ2 Systems

PhICl2Sterically hindered ArICl2
2,4,6-tri-isopropylphenylICl2PhI(OAc)2

Structures of R2W-X Systems (W=B...Tl, X=F...I)

R2B-F System, showing single asymmetric bridgeR2Ga-F, showing symmetric dimer
R2In-F symmetric trimerR2In-F, showing a dimeric ladder, and slight asymmetry
R2In-Cl, showing symmetric dimerR2In-Cl, showing sterically hindered monomer
R2In-Br, showing unsymmetric dimerR2In-Br, showing sterically hindered monomer
R2Ga-I symmetric dimerR2In-I symmetric dimer
R2Tl-Cl unsymmetric dimerR2Tl-Cl unsymmetric dimer