Stereochemical Consequences of Oxygen Atom Transfer and Electron Transfer in Imido/Oxido Molybdenum(IV, V, VI) Complexes with Two Unsymmetric Bidentate Ligands

Autoren

Kristina Hüttinger
Christoph Förster
Timo Bund
Dariush Hinderberger
Katja Heinze

DOI

10.1021/ic202588u

eISSN

1520-510X

ISSN

0020-1669

Ausgabe der Veröffentlichung

7

Zeitschrift

Inorganic Chemistry

Sprache

en

Online publication date

2012

Paginierung

4180 - 4192

Datum der Veröffentlichung

2012

Status

Published

Herausgeber

American Chemical Society (ACS)

Herausgeber URL

http://dx.doi.org/10.1021/ic202588u

Datum der Datenerfassung

2024

Titel

Stereochemical Consequences of Oxygen Atom Transfer and Electron Transfer in Imido/Oxido Molybdenum(IV, V, VI) Complexes with Two Unsymmetric Bidentate Ligands

Ausgabe der Zeitschrift

51

Data source: Crossref

Abstract

Two equivalents of the unsymmetrical Schiff base ligand (L(tBu))(-) (4-tert-butyl phenyl(pyrrolato-2-ylmethylene)amine) and MoCl(2)(NtBu)O(dme) (dme = 1,2-dimethoxyethane) gave a single stereoisomer of a mixed imido/oxido Mo(VI) complex 2(tBu). The stereochemistry of 2(tBu) was elucidated using X-ray diffraction, NMR spectroscopy, and DFT calculations. The complex is active in an oxygen atom transfer (OAT) reaction to trimethyl phosphane. The putative intermediate five-coordinate Mo(IV) imido complex coordinates a PMe(3) ligand, giving the six-coordinate imido phosphane Mo(IV) complex 5(tBu). The stereochemistry of 5(tBu) is different from that of 2(tBu) as shown by NMR spectroscopy, DFT calculations, and X-ray diffraction. Single-electron oxidation of 5(tBu) with ferrocenium hexafluorophosphate gave the stable cationic imido phosphane Mo(V) complex [5(tBu)](+) as the PF(6)(-) salt. EPR spectra of [5(tBu)](PF(6)) confirmed the presence of PMe(3) in the coordination sphere. Single-crystal X-ray diffraction analysis of [5(tBu)](PF(6)) revealed that electron transfer occurred under retention of the stereochemical configuration. The rate of OAT, the outcome of the electron transfer reaction, and the stabilities of the imido complexes presented here differ dramatically from those of analogous oxido complexes.

Addresses

Institute of Inorganic Chemistry and Analytical Chemistry, Johannes Gutenberg-University of Mainz, Duesbergweg 10-14, 55128 Mainz, Germany.

Autoren

Kristina Hüttinger
Christoph Förster
Timo Bund
Dariush Hinderberger
Katja Heinze

DOI

10.1021/ic202588u

eISSN

1520-510X

Externe Identifier

PubMed Identifier: 22432605

Open access

false

ISSN

0020-1669

Ausgabe der Veröffentlichung

7

Zeitschrift

Inorganic chemistry

Schlüsselwörter

Oxygen
Molybdenum
Ferrous Compounds
Ethyl Ethers
Schiff Bases
Ligands
Crystallography, X-Ray
Magnetic Resonance Spectroscopy
Molecular Structure
Electron Transport
Oxidation-Reduction
Stereoisomerism
Electrons
Quantum Theory
Models, Molecular
Coordination Complexes

Sprache

eng

Medium

Print-Electronic

Online publication date

2012

Paginierung

4180 - 4192

Datum der Veröffentlichung

2012

Status

Published

Datum der Datenerfassung

2012

Titel

Stereochemical consequences of oxygen atom transfer and electron transfer in imido/oxido molybdenum(IV, V, VI) complexes with two unsymmetric bidentate ligands.

Sub types

Research Support, Non-U.S. Gov't
Journal Article

Ausgabe der Zeitschrift

51

Data source: Europe PubMed Central

Abstract

Two equivalents of the unsymmetrical Schiff base ligand (L(tBu))(-) (4-tert-butyl phenyl(pyrrolato-2-ylmethylene)amine) and MoCl(2)(NtBu)O(dme) (dme = 1,2-dimethoxyethane) gave a single stereoisomer of a mixed imido/oxido Mo(VI) complex 2(tBu). The stereochemistry of 2(tBu) was elucidated using X-ray diffraction, NMR spectroscopy, and DFT calculations. The complex is active in an oxygen atom transfer (OAT) reaction to trimethyl phosphane. The putative intermediate five-coordinate Mo(IV) imido complex coordinates a PMe(3) ligand, giving the six-coordinate imido phosphane Mo(IV) complex 5(tBu). The stereochemistry of 5(tBu) is different from that of 2(tBu) as shown by NMR spectroscopy, DFT calculations, and X-ray diffraction. Single-electron oxidation of 5(tBu) with ferrocenium hexafluorophosphate gave the stable cationic imido phosphane Mo(V) complex [5(tBu)](+) as the PF(6)(-) salt. EPR spectra of [5(tBu)](PF(6)) confirmed the presence of PMe(3) in the coordination sphere. Single-crystal X-ray diffraction analysis of [5(tBu)](PF(6)) revealed that electron transfer occurred under retention of the stereochemical configuration. The rate of OAT, the outcome of the electron transfer reaction, and the stabilities of the imido complexes presented here differ dramatically from those of analogous oxido complexes.

Autoren

Kristina Hüttinger
Christoph Förster
Timo Bund
Dariush Hinderberger
Katja Heinze

Autoren-URL

https://www.ncbi.nlm.nih.gov/pubmed/22432605

DOI

10.1021/ic202588u

eISSN

1520-510X

Ausgabe der Veröffentlichung

7

Zeitschrift

Inorg Chem

Schlüsselwörter

Coordination Complexes
Crystallography, X-Ray
Electron Transport
Electrons
Ethyl Ethers
Ferrous Compounds
Ligands
Magnetic Resonance Spectroscopy
Models, Molecular
Molecular Structure
Molybdenum
Oxidation-Reduction
Oxygen
Quantum Theory
Schiff Bases
Stereoisomerism

Sprache

eng

Country

United States

Paginierung

4180 - 4192

Datum der Veröffentlichung

2012

Status

Published

Datum, an dem der Datensatz öffentlich gemacht wurde

2012

Titel

Stereochemical consequences of oxygen atom transfer and electron transfer in imido/oxido molybdenum(IV, V, VI) complexes with two unsymmetric bidentate ligands.

Sub types

Journal Article
Research Support, Non-U.S. Gov't

Ausgabe der Zeitschrift

51

Data source: PubMed

Stereochemical Consequences of Oxygen Atom Transfer and Electron Transfer in Imido/Oxido Molybdenum(IV, V, VI) Complexes with Two Unsymmetric Bidentate Ligands

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