TY - JOUR
T1 - Theoretical evidence of persistent chirality in D3 homoleptic hexacoordinate complexes with monodentate ligands
AU - Alemany, Pere
AU - Alvarez, Santiago
AU - Avnir, David
PY - 2003/5/9
Y1 - 2003/5/9
N2 - 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 C6H4-4-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(SC6H4-4-OMe)6]2- indicate that a larger barrier should be expected. For the chiral homoleptic organometallic complexes [ZrMe6]2- and [RhMe6]3- no significant racemization barrier is expected.
AB - 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 C6H4-4-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(SC6H4-4-OMe)6]2- indicate that a larger barrier should be expected. For the chiral homoleptic organometallic complexes [ZrMe6]2- and [RhMe6]3- no significant racemization barrier is expected.
KW - Bailar twist
KW - Chirality
KW - Coordination chemistry
KW - Density functional calculations
UR - http://www.scopus.com/inward/record.url?scp=0038664351&partnerID=8YFLogxK
U2 - 10.1002/chem.200204485
DO - 10.1002/chem.200204485
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AN - SCOPUS:0038664351
SN - 0947-6539
VL - 9
SP - 1952
EP - 1957
JO - Chemistry - A European Journal
JF - Chemistry - A European Journal
IS - 9
ER -