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Mesomerization of S 4 ‐Symmetric Tetrahedral Chelate Complex [In 4 (L 3 ) 4 ]: First‐Time Monitored by Temperature‐Dependent 1 H NMR Spectroscopy
Author(s) -
Saalfrank Rolf W.,
Maid Harald,
Scheurer Andreas,
Puchta Ralph,
Bauer Walter
Publication year - 2010
Publication title -
european journal of inorganic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.667
H-Index - 136
eISSN - 1099-0682
pISSN - 1434-1948
DOI - 10.1002/ejic.201000295
Subject(s) - chemistry , isomerization , indium , crystallography , nuclear magnetic resonance spectroscopy , spectroscopy , stereochemistry , catalysis , physics , biochemistry , organic chemistry , quantum mechanics
VT 1 H NMR spectroscopy proved that a non‐dissociative and reversible mesomerization process links the tetranuclear indium(III) complexes meso ‐(Δ,Δ,Λ,Λ)( P , P , M , M )‐ 3 and meso ‐(Λ,Λ,Δ,Δ)( M , M , P , P )‐ 3′ . During this process four tandem Bailar twists, resulting in the (Δ)/(Λ) isomerization at the indium centers, and the ( P )/( M ) inversion of the four coordinating face‐centered, helical ligands (L 3 ) 3– are involved. In addition, gas‐phase DFT calculations (B3LYP/LANL2DZp) revealed a C 1 ‐symmetric transition state (+21.9 kcal mol –1 ) for the mesomerization mechanism which connects 3 and 3′ .