ja960385e_si_001.html (0.59 kB)
Dynamic Pathways for Fluxional Molecules Defined Using Exchange-NOE Peaks
dataset
posted on 1996-08-14, 00:00 authored by Enzo Alessio, Lory Hansen, Marian Iwamoto, Luigi G. MarzilliIn examining NMR methods to assess orientation and
fluxional motions of planar N-donor heterocyclic
coordinated ligands (L's) in solution, we introduce the use of
exchange-NOE NMR data as a powerful method for
defining (i) the extent of L rotation about the metal-N bond, (ii) the
direction of L rotation, and (iii) even the halves
of C2-symmetrical L's that interchange during
dynamic processes. The full value of the approach depends on
a
strategy in which the complexes studied are chiral and similar except
that one has a lopsided L (Me3Bzm =
1,5,6-trimethylbenzimidazole in
[Re2O3Cl4(Me3Bzm)4]
(1)) and the other has a
C2-symmetrical L (3,5-lut =
3,5-lutidine
in
[Re2O3Cl4(3,5-lut)4]
(2)). Each Re is part of a nearly linear
ORe−O−ReO grouping and has a “terminal” L
(Lt) and a stacked L (Ls). The fluxional
inversion of the two chiral dimers involves rotations of ∼180°
about the
Re−O−Re bonds and of ∼90° about all four Re−L bonds. The
exchange-NOE data for 2 show that the half of
Lt
away from the dimer center interchanges with the half of Ls
close to the center, with the L plane rotating past the
ORe−O bonds, not the N−Re−Cl bonds. Thus, the
exchange-NOE data help to establish the direction of L
rotation. In 1, Me3Bzmt
has the rare head-to-head (HH) orientation with respect to the partner.
This partner Me3Bzms stacks with the Me3Bzms
from the other Re in the common head-to-tail (HT) orientation.
Compelling evidence
that the predominant solution conformer of 1 has the
HH,HT,HH structure includes unusual chemical shift
dispersions
and a strong interligand NOE cross-peak. This is the only case in
which cis,bis imidazole-ring-ligated
untethered
ligands have been found to be predominantly HH in solution. This
predominance can be attributed to the electrostatic
attraction of the δ+ N2C proton for the
negative core of the molecule (bridging O, cis Cl on same
Re, and two cis
Cl's on the other Re).