Configuration Control in the Synthesis of Homo- and Heteroleptic Bis(oxazolinylphenolato/thiazolinylphenolato)
Chelate Ligand Complexes of Oxorhenium(V): Isomer Effect on Ancillary
Ligand Exchange Dynamics and Implications for Perchlorate Reduction
Catalysis
Jinyong Liu
Dimao Wu
Xiaoge Su
Mengwei Han
Susana Y. Kimura
Danielle
L. Gray
John R. Shapley
Mahdi M. Abu-Omar
Charles J. Werth
Timothy J. Strathmann
10.1021/acs.inorgchem.5b02940.s002
https://acs.figshare.com/articles/dataset/Configuration_Control_in_the_Synthesis_of_Homo_and_Heteroleptic_Bis_oxazolinylphenolato_thiazolinylphenolato_Chelate_Ligand_Complexes_of_Oxorhenium_V_Isomer_Effect_on_Ancillary_Ligand_Exchange_Dynamics_and_Implications_for_Perchlorate_Reduction_Catalysis/2429644
This
study develops synthetic strategies for N,N-<i>trans</i> and N,N-<i>cis</i> Re(O)(<i>L</i><sub>O–N</sub>)<sub>2</sub>Cl complexes and investigates the effects of the coordination
spheres and ligand structures on ancillary ligand exchange dynamics
and catalytic perchlorate reduction activities of the corresponding
[Re(O)(<i>L</i><sub>O–N</sub>)<sub>2</sub>]<sup>+</sup> cations. The 2-(2′-hydroxyphenyl)-2-oxazoline (H<i>hoz</i>) and 2-(2′-hydroxyphenyl)-2-thiazoline (H<i>htz</i>) ligands are used to prepare homoleptic N,N-<i>trans</i> and N,N-<i>cis</i> isomers of both Re(O)(<i>hoz</i>)<sub>2</sub>Cl and Re(O)(<i>htz</i>)<sub>2</sub>Cl and
one heteroleptic N,N-<i>trans</i> Re(O)(<i>hoz</i>)(<i>htz</i>)Cl. Selection of <i>hoz</i>/<i>htz</i> ligands determines the preferred isomeric coordination
sphere, and the use of substituted pyridine bases with varying degrees
of steric hindrance during complex synthesis controls the rate of
isomer interconversion. The five corresponding [Re(O)(<i>L</i><sub>O–N</sub>)<sub>2</sub>]<sup>+</sup> cations exhibit a
wide range of solvent exchange rates (1.4 to 24,000 s<sup>–1</sup> at 25 °C) and different <i>L</i><sub>O–N</sub> movement patterns, as influenced by the coordination sphere of Re
(<i>trans</i>/<i>cis</i>), the noncoordinating
heteroatom on <i>L</i><sub>O–N</sub> ligands (O/S),
and the combination of the two <i>L</i><sub>O–N</sub> ligands (homoleptic/heteroleptic). Ligand exchange dynamics also
correlate with the activity of catalytic reduction of aqueous ClO<sub>4</sub><sup>–</sup> by H<sub>2</sub> when the Re(O)(<i>L</i><sub>O–N</sub>)<sub>2</sub>Cl complexes are immobilized
onto Pd/C. Findings from this study provide novel synthetic strategies
and mechanistic insights for innovations in catalytic, environmental,
and biomedical research.
2016-02-19 00:00:00
Ancillary Ligand Exchange Dynamics
isomeric coordination sphere
coordination spheres
ligand structures
H 2
isomer interconversion
noncoordinating heteroatom
ligand exchange dynamics
Perchlorate Reduction CatalysisThis study
steric hindrance
perchlorate reduction activities
LO
synthesis controls
coordination sphere
pyridine bases
Configuration Control