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

Three Re(I) tricarbonyl complexes, with the general formulation Re(N^L)(CO)3X (where N^L is a bidentate ligand containing a pyridine functionalized at position 2 with a thione or a thiazol-2-ylidene group and X is either chloro or bromo), were synthesized and their reactivities explored in terms of...

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Main Authors: Stout, Matthew J., Skelton, B.W., Sobolev, Alexandre N., Raiteri, Paolo, Massi, Max, Simpson, Peter
Format: Journal Article
Language:English
Published: AMER CHEMICAL SOC 2020
Subjects:
Online Access:http://hdl.handle.net/20.500.11937/84771
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author Stout, Matthew J.
Skelton, B.W.
Sobolev, Alexandre N.
Raiteri, Paolo
Massi, Max
Simpson, Peter
author_facet Stout, Matthew J.
Skelton, B.W.
Sobolev, Alexandre N.
Raiteri, Paolo
Massi, Max
Simpson, Peter
author_sort Stout, Matthew J.
building Curtin Institutional Repository
collection Online Access
description Three Re(I) tricarbonyl complexes, with the general formulation Re(N^L)(CO)3X (where N^L is a bidentate ligand containing a pyridine functionalized at position 2 with a thione or a thiazol-2-ylidene group and X is either chloro or bromo), were synthesized and their reactivities explored in terms of solvent-dependent ligand substitution, in both the ground and excited states. When they were dissolved in acetonitrile, the complexes bound to the thione ligand underwent reversible ligand exchange with the solvent, resulting in the formation of Re(NCMe)2(CO)3X; the starting complex could be re-formed by precipitation following addition of diethyl ether. On the other hand, the complexes appeared to be inert in dichloromethane or acetone. Conversely, the complex bound to the thiazol-2-ylidene ligand did not display any ligand exchange reaction in the dark but underwent photoactivated ligand substitution on excitation 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 thiazol-2-ylidene ligand.
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spelling curtin-20.500.11937-847712021-08-12T02:30:52Z Synthesis and Photochemical Properties of Re(I) Tricarbonyl Complexes Bound to Thione and Thiazol-2-ylidene Ligands Stout, Matthew J. Skelton, B.W. Sobolev, Alexandre N. Raiteri, Paolo Massi, Max Simpson, Peter Science & Technology Physical Sciences Chemistry, Inorganic & Nuclear Chemistry, Organic Chemistry HETEROCYCLIC CARBENE COMPLEXES POLYPYRIDINE COMPLEXES LUMINESCENT RHENIUM(I) REDUCTION CO2 PHOTOLUMINESCENCE PHOTOPHYSICS REACTIVITY REAGENTS PROBES Three Re(I) tricarbonyl complexes, with the general formulation Re(N^L)(CO)3X (where N^L is a bidentate ligand containing a pyridine functionalized at position 2 with a thione or a thiazol-2-ylidene group and X is either chloro or bromo), were synthesized and their reactivities explored in terms of solvent-dependent ligand substitution, in both the ground and excited states. When they were dissolved in acetonitrile, the complexes bound to the thione ligand underwent reversible ligand exchange with the solvent, resulting in the formation of Re(NCMe)2(CO)3X; the starting complex could be re-formed by precipitation following addition of diethyl ether. On the other hand, the complexes appeared to be inert in dichloromethane or acetone. Conversely, the complex bound to the thiazol-2-ylidene ligand did not display any ligand exchange reaction in the dark but underwent photoactivated ligand substitution on excitation 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 thiazol-2-ylidene ligand. 2020 Journal Article http://hdl.handle.net/20.500.11937/84771 10.1021/acs.organomet.0c00381 English AMER CHEMICAL SOC restricted
spellingShingle Science & Technology
Physical Sciences
Chemistry, Inorganic & Nuclear
Chemistry, Organic
Chemistry
HETEROCYCLIC CARBENE COMPLEXES
POLYPYRIDINE COMPLEXES
LUMINESCENT RHENIUM(I)
REDUCTION
CO2
PHOTOLUMINESCENCE
PHOTOPHYSICS
REACTIVITY
REAGENTS
PROBES
Stout, Matthew J.
Skelton, B.W.
Sobolev, Alexandre N.
Raiteri, Paolo
Massi, Max
Simpson, Peter
Synthesis and Photochemical Properties of Re(I) Tricarbonyl Complexes Bound to Thione and Thiazol-2-ylidene Ligands
title Synthesis and Photochemical Properties of Re(I) Tricarbonyl Complexes Bound to Thione and Thiazol-2-ylidene Ligands
title_full Synthesis and Photochemical Properties of Re(I) Tricarbonyl Complexes Bound to Thione and Thiazol-2-ylidene Ligands
title_fullStr Synthesis and Photochemical Properties of Re(I) Tricarbonyl Complexes Bound to Thione and Thiazol-2-ylidene Ligands
title_full_unstemmed Synthesis and Photochemical Properties of Re(I) Tricarbonyl Complexes Bound to Thione and Thiazol-2-ylidene Ligands
title_short Synthesis and Photochemical Properties of Re(I) Tricarbonyl Complexes Bound to Thione and Thiazol-2-ylidene Ligands
title_sort synthesis and photochemical properties of re(i) tricarbonyl complexes bound to thione and thiazol-2-ylidene ligands
topic Science & Technology
Physical Sciences
Chemistry, Inorganic & Nuclear
Chemistry, Organic
Chemistry
HETEROCYCLIC CARBENE COMPLEXES
POLYPYRIDINE COMPLEXES
LUMINESCENT RHENIUM(I)
REDUCTION
CO2
PHOTOLUMINESCENCE
PHOTOPHYSICS
REACTIVITY
REAGENTS
PROBES
url http://hdl.handle.net/20.500.11937/84771