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Synthesis and Photochemical Properties of Re(I) Tricarbonyl Complexes Bound to Thione and Thiazole-2-ylidene Ligands

preprint
submitted on 19.05.2020 and posted on 19.05.2020 by Matthew Stout, Brian Skelton, Alexandre N. Sobolev, Paolo Raiteri, Massimiliano Massi, Peter Simpson

Three Re(I) tricarbonyl complexes, with general formulation Re(N^L)(CO)3X (where N^L is a bidentate ligand containing a pyridine functionalized in the position 2 with a thione or a thiazol-2-ylidene group and X is either chloro or bromo) were synthesized and their reactivity explored in terms of solvent-dependent ligand substitution, both in the ground and excited states. When dissolved in acetonitrile, the complexes bound to the thione ligand underwent ligand exchange with the solvent resulting in the formation of Re(NCMe)2(CO)3X. The exchange was found to be reversible, and the starting complex was reformed upon removal of the solvent. On the other hand, the complexes appeared inert in dichloromethane or acetone. Conversely, the complex bound to the thiazole-2-ylidene ligand did not display any ligand exchange reaction in the dark, but underwent photoactivated ligand substitution when excited to its lowest metal-to-ligand charge transfer manifold. Photolysis of this complex in acetonitrile generated multiple products, including Re(I) tricarbonyl and dicarbonyl solvato-complexes as well as free thiazole-2-ylidene ligand.

History

Email Address of Submitting Author

m.massi@curtin.edu.au

Institution

Curtin University

Country

Australia

ORCID For Submitting Author

0000-0001-6949-4019

Declaration of Conflict of Interest

nothing to declare

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