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Theoretical Evidence of Persistent Chirality in D 3 Homoleptic Hexacoordinate Complexes with Monodentate Ligands
Author(s) -
Alemany Pere,
Alvarez Santiago,
Avnir David
Publication year - 2003
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.200204485
Subject(s) - hexacoordinate , homoleptic , denticity , chirality (physics) , chemistry , crystallography , stereochemistry , organic chemistry , crystal structure , physics , metal , nambu–jona lasinio model , chiral symmetry breaking , quantum mechanics , silicon , quark
A theoretical study of the enantiomer interconversion pathway relevant to racemization reactions of hexacoordinate transition‐metal complexes is presented based on density functional calculations. The potential‐energy surface for the trigonal twist pathway of the [Zr(SH) 6 ] 2− model compound has been explored. The optimum structure reproduces, to a very good approximation, the experimental geometry of the analogous compound in which the thiolato groups have C 6 H 4 ‐4‐OMe substituents instead of H atoms. A barrier of about 19 kcal mol −1 is estimated for the racemization of [Zr(SH) 6 ] 2− and exploratory calculations for [Zr(SC 6 H 4 ‐4‐OMe) 6 ] 2− indicate that a larger barrier should be expected. For the chiral homoleptic organometallic complexes [ZrMe 6 ] 2− and [RhMe 6 ] 3− no significant racemization barrier is expected.