Fully Solvated, Monomeric ReII Complexes: Insights into the Chemistry of [Re(NCCH3)6]2+
- Robin BolligerRobin BolligerDepartment of Chemistry, University of Zurich, Winterthurerstrasse 190, 8057 Zürich, SwitzerlandMore by Robin Bolliger
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- Giuseppe MeolaGiuseppe MeolaDepartment of Chemistry, University of Zurich, Winterthurerstrasse 190, 8057 Zürich, SwitzerlandMore by Giuseppe Meola
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- Henrik BrabandHenrik BrabandDepartment of Chemistry, University of Zurich, Winterthurerstrasse 190, 8057 Zürich, SwitzerlandMore by Henrik Braband
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- Olivier BlacqueOlivier BlacqueDepartment of Chemistry, University of Zurich, Winterthurerstrasse 190, 8057 Zürich, SwitzerlandMore by Olivier Blacque
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- Lukas SiebenmannLukas SiebenmannDepartment of Chemistry, University of Zurich, Winterthurerstrasse 190, 8057 Zürich, SwitzerlandMore by Lukas Siebenmann
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- Qaisar NadeemQaisar NadeemDepartment of Chemistry, University of Zurich, Winterthurerstrasse 190, 8057 Zürich, SwitzerlandMore by Qaisar Nadeem
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- Roger Alberto*Roger Alberto*(R.A.) Email: [email protected]Department of Chemistry, University of Zurich, Winterthurerstrasse 190, 8057 Zürich, SwitzerlandMore by Roger Alberto
Abstract
The oxidation of [Re(η6-C10H8)2]+ with AgI in acetonitrile yields [Re(NCCH3)6]2+. This fully solvated ReII compound was characterized by spectroscopic methods and X-ray structure analyses. We show that [Re(NCCH3)6]2+ acts as a precursor complex for a variety of substitution reactions. Treatment with monodentate triphenylphosphine (PPh3) and bidentate 1,2-bis(diphenylphosphino)ethane (dppe) yields the complexes [trans-Re(PPh3)2(NCCH3)4]2+ and [trans-Re(dppe)2(NCCH3)2]+, respectively. [trans-Re(dppe)2(NCCH3)2]+ is oxidized under mild conditions by AgI to its ReII analogue [trans-Re(dppe)2(NCCH3)2]2+. Reactions of [Re(NCCH3)6]2+ with a halide mixture consisting of NaX and AgX (X = Cl, I) result in the formation of the corresponding ReIII complexes [trans-ReX2(NCCH3)4]+. [trans-ReBr2(NCCH3)4]+ can be obtained directly from [Re(η6-C10H8)2]+ by oxidation with FeBr3 in acetonitrile. The title compound is thus a convenient starting material for ReII and ReIII complexes by simple solvent exchange, which are otherwise difficult to access.
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