Spectroscopic Characterization of a Monomeric, Cyclopentadienyl-Based Rhenium(V) Dioxo Complex

Suresh Raju; Johann T. B. H. Jastrzebski; Martin Lutz; Léon Witteman; Johannes Rytter Dethlefsen; Peter Fristrup; Marc-Etienne Moret; Robertus J. M. Klein Gebbink

doi:10.1021/acs.inorgchem.5b02366

Spectroscopic Characterization of a Monomeric, Cyclopentadienyl-Based Rhenium(V) Dioxo Complex

Suresh Raju
, Johann T. B. H. Jastrzebski
, Martin Lutz
, Léon Witteman
, Johannes Rytter Dethlefsen
, Peter Fristrup
, Marc-Etienne Moret
, Robertus J. M. Klein Gebbink

Department of Chemistry

Utrecht University

Research output: Contribution to journal › Journal article › Research › peer-review

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Abstract

Mononuclear, coordinatively unsaturated rhenium(V) dioxo species of the type XReO₂(X = Me, substituted cyclopentadienyl) have long been postulated as intermediates in rhenium-catalyzed deoxydehydration, but their characterization was precluded because of aggregation into dimeric or oligomeric structures. Using the bulky 1,2,4-tri-tert-butylcyclopentadienyl (Cp^ttt) ligand, the rhenium(V) dioxo species (Cp^ttt)ReO₂ could now be observed, in equilibrium with the dimeric form [(Cp^ttt)Re(O)μ-O]₂, and characterized by NMR, IR, and UV-vis spectroscopies, as well as electrospray ionization mass spectrometry. (Cp^ttt)ReO₂ is shown to be the primary product of reduction of the rhenium(VII) complex (Cp^ttt)ReO₃ with PPh₃ and demonstrated to react with ethylene glycol significantly faster than its dimeric counterpart, supporting its role as an intermediate in rhenium-catalyzed deoxydehydration reactions.

Original language	English
Journal	Inorganic Chemistry
Volume	54
Issue number	22
Pages (from-to)	11031-11036
Number of pages	6
ISSN	0020-1669
DOIs	https://doi.org/10.1021/acs.inorgchem.5b02366
Publication status	Published - 2015

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This is an open access article published under an ACS AuthorChoice License, which permits copying and redistribution of the article or any adaptations for non-commercial purposes.

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@article{c267c947d1634303a866314035065472,

title = "Spectroscopic Characterization of a Monomeric, Cyclopentadienyl-Based Rhenium(V) Dioxo Complex",

abstract = "Mononuclear, coordinatively unsaturated rhenium(V) dioxo species of the type XReO2 (X = Me, substituted cyclopentadienyl) have long been postulated as intermediates in rhenium-catalyzed deoxydehydration, but their characterization was precluded because of aggregation into dimeric or oligomeric structures. Using the bulky 1,2,4-tri-tert-butylcyclopentadienyl (Cpttt) ligand, the rhenium(V) dioxo species (Cpttt)ReO2 could now be observed, in equilibrium with the dimeric form [(Cpttt)Re(O)μ-O]2, and characterized by NMR, IR, and UV-vis spectroscopies, as well as electrospray ionization mass spectrometry. (Cpttt)ReO2 is shown to be the primary product of reduction of the rhenium(VII) complex (Cpttt)ReO3 with PPh3 and demonstrated to react with ethylene glycol significantly faster than its dimeric counterpart, supporting its role as an intermediate in rhenium-catalyzed deoxydehydration reactions. ",

author = "Suresh Raju and Jastrzebski, \{Johann T. B. H.\} and Martin Lutz and L{\'e}on Witteman and Dethlefsen, \{Johannes Rytter\} and Peter Fristrup and Marc-Etienne Moret and Gebbink, \{Robertus J. M. Klein\}",

note = "This is an open access article published under an ACS AuthorChoice License, which permits copying and redistribution of the article or any adaptations for non-commercial purposes.",

year = "2015",

doi = "10.1021/acs.inorgchem.5b02366",

language = "English",

volume = "54",

pages = "11031--11036",

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T1 - Spectroscopic Characterization of a Monomeric, Cyclopentadienyl-Based Rhenium(V) Dioxo Complex

AU - Raju, Suresh

AU - Jastrzebski, Johann T. B. H.

AU - Lutz, Martin

AU - Witteman, Léon

AU - Dethlefsen, Johannes Rytter

AU - Fristrup, Peter

AU - Moret, Marc-Etienne

AU - Gebbink, Robertus J. M. Klein

N1 - This is an open access article published under an ACS AuthorChoice License, which permits copying and redistribution of the article or any adaptations for non-commercial purposes.

PY - 2015

Y1 - 2015

N2 - Mononuclear, coordinatively unsaturated rhenium(V) dioxo species of the type XReO2 (X = Me, substituted cyclopentadienyl) have long been postulated as intermediates in rhenium-catalyzed deoxydehydration, but their characterization was precluded because of aggregation into dimeric or oligomeric structures. Using the bulky 1,2,4-tri-tert-butylcyclopentadienyl (Cpttt) ligand, the rhenium(V) dioxo species (Cpttt)ReO2 could now be observed, in equilibrium with the dimeric form [(Cpttt)Re(O)μ-O]2, and characterized by NMR, IR, and UV-vis spectroscopies, as well as electrospray ionization mass spectrometry. (Cpttt)ReO2 is shown to be the primary product of reduction of the rhenium(VII) complex (Cpttt)ReO3 with PPh3 and demonstrated to react with ethylene glycol significantly faster than its dimeric counterpart, supporting its role as an intermediate in rhenium-catalyzed deoxydehydration reactions.

AB - Mononuclear, coordinatively unsaturated rhenium(V) dioxo species of the type XReO2 (X = Me, substituted cyclopentadienyl) have long been postulated as intermediates in rhenium-catalyzed deoxydehydration, but their characterization was precluded because of aggregation into dimeric or oligomeric structures. Using the bulky 1,2,4-tri-tert-butylcyclopentadienyl (Cpttt) ligand, the rhenium(V) dioxo species (Cpttt)ReO2 could now be observed, in equilibrium with the dimeric form [(Cpttt)Re(O)μ-O]2, and characterized by NMR, IR, and UV-vis spectroscopies, as well as electrospray ionization mass spectrometry. (Cpttt)ReO2 is shown to be the primary product of reduction of the rhenium(VII) complex (Cpttt)ReO3 with PPh3 and demonstrated to react with ethylene glycol significantly faster than its dimeric counterpart, supporting its role as an intermediate in rhenium-catalyzed deoxydehydration reactions.

U2 - 10.1021/acs.inorgchem.5b02366

DO - 10.1021/acs.inorgchem.5b02366

M3 - Journal article

C2 - 26517008

SN - 0020-1669

VL - 54

SP - 11031

EP - 11036

JO - Inorganic Chemistry

JF - Inorganic Chemistry

IS - 22

ER -

Spectroscopic Characterization of a Monomeric, Cyclopentadienyl-Based Rhenium(V) Dioxo Complex

Abstract

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