Oxorhenium(V) complexes with N,O-multidentate ligands have been recognized as versatile catalysts for synthetic, energy, and environmental applications. Very recently we have identified vastly different rates (e.g., ranging from 1.4 to 24,000 s-1 at 25 ○C) and styles of ligand exchange of the two LO-N ligands in N,N-trans and N,N-cis Re(O)(LO-N)2X isomers. With the same Re coordination sphere, the ligand exchange kinetics can also be tuned through ligand structure modification and the homoleptic/heteroleptic coordination design. From a survey of all previously reported N,N-trans and N,N-cis Re(O)(LO-N)2X crystal structures, we identified an interesting trend of the dihedral angles between the two LO-N ligands in most N,N-trans (&gt;90○) and N,N-cis (&lt;90○) structures. This trend inspired the rapid and selective synthesis of a series of new N,N-trans Re(O)(LO-N)2X structures by structural modification of LO-N ligands. Implications of selectively preparing N,N-cis Re(O)(LO-N)2X structures was also obtained by DFT calculation. Beyond the insights in Re coordination chemistry, these studies will also illuminate the development of oxotechnetium(V) complexes for radiopharmaceutical applications. Results of perchlorate reduction by our Re(O)(LO-N)2Cl catalyst precursors in homogeneous solution and in heterogeneous carbon support will also be presented.

Ligand exchange dynamics and controlled synthesis of isomeric oxorhenium(V) complexes

254th National Meeting (2017)

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