Solvent-dependent interconversions between Rhi, RhII, and RhIII complexes of an aryl-monophosphine ligand

Michael Montage; Gregory Leitus; Linda J.W. Shimon; Yehoshoa Ben-David; David Milstein

doi:10.1002/chem.200700805

Solvent-dependent interconversions between Rhⁱ, Rh^II, and Rh^III complexes of an aryl-monophosphine ligand

Michael Montage, Gregory Leitus, Linda J.W. Shimon, Yehoshoa Ben-David, David Milstein

Weizmann Institute of Science, Israel

Research output: Contribution to journal › Article › peer-review

18 Citations (Scopus)

Abstract

Reaction of the aryl-monophosphine ligand α²- (diisopropylphosphino)isodurene (1) with the Rh^I precursor [Rh(coe)₂(acetone)₂]BF₄ (coe = cyclooctene) in different solvents yielded complexes of all three common oxidation states of rhodium, depending on the solvent used. When the reaction was carried out in methanol a cyclometalated, solvent-stabilized Rh^IIIalkylhydride complex (2) was obtained. However, when the reaction was carried out in acetone or dichloromethane a dinuclear η⁶-arene Rh^II complex (5) was obtained in the absence of addedredox reagents. Moreover, when acetonitrile was added to a solution of either the Rh^II or Rh ^III complexes, a new solvent-stabilized, noncyclometalated Rh ^I complex (6) was obtained. In this report we describe the different complexes, which were fully characterized, and probe the processes behind the remarkable solvent effect observed.

Original language	English
Pages (from-to)	9043-9055
Number of pages	13
Journal	Chemistry - A European Journal
Volume	13
Issue number	32
DOIs	https://doi.org/10.1002/chem.200700805
Publication status	Published - Nov 19 2007

Keywords

Arene complexes
C-H activation
Oxidation state
Phosphanes
Rhodium
Solvent effects

ASJC Scopus subject areas

Catalysis
Organic Chemistry

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title = "Solvent-dependent interconversions between Rhi, RhII, and RhIII complexes of an aryl-monophosphine ligand",

abstract = "Reaction of the aryl-monophosphine ligand α2- (diisopropylphosphino)isodurene (1) with the RhI precursor [Rh(coe)2(acetone)2]BF4 (coe = cyclooctene) in different solvents yielded complexes of all three common oxidation states of rhodium, depending on the solvent used. When the reaction was carried out in methanol a cyclometalated, solvent-stabilized RhIIIalkylhydride complex (2) was obtained. However, when the reaction was carried out in acetone or dichloromethane a dinuclear η6-arene RhII complex (5) was obtained in the absence of addedredox reagents. Moreover, when acetonitrile was added to a solution of either the RhII or Rh III complexes, a new solvent-stabilized, noncyclometalated Rh I complex (6) was obtained. In this report we describe the different complexes, which were fully characterized, and probe the processes behind the remarkable solvent effect observed.",

keywords = "Arene complexes, C-H activation, Oxidation state, Phosphanes, Rhodium, Solvent effects",

author = "Michael Montage and Gregory Leitus and Shimon, {Linda J.W.} and Yehoshoa Ben-David and David Milstein",

year = "2007",

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AU - Montage, Michael

AU - Leitus, Gregory

AU - Shimon, Linda J.W.

AU - Ben-David, Yehoshoa

AU - Milstein, David

PY - 2007/11/19

Y1 - 2007/11/19

N2 - Reaction of the aryl-monophosphine ligand α2- (diisopropylphosphino)isodurene (1) with the RhI precursor [Rh(coe)2(acetone)2]BF4 (coe = cyclooctene) in different solvents yielded complexes of all three common oxidation states of rhodium, depending on the solvent used. When the reaction was carried out in methanol a cyclometalated, solvent-stabilized RhIIIalkylhydride complex (2) was obtained. However, when the reaction was carried out in acetone or dichloromethane a dinuclear η6-arene RhII complex (5) was obtained in the absence of addedredox reagents. Moreover, when acetonitrile was added to a solution of either the RhII or Rh III complexes, a new solvent-stabilized, noncyclometalated Rh I complex (6) was obtained. In this report we describe the different complexes, which were fully characterized, and probe the processes behind the remarkable solvent effect observed.

AB - Reaction of the aryl-monophosphine ligand α2- (diisopropylphosphino)isodurene (1) with the RhI precursor [Rh(coe)2(acetone)2]BF4 (coe = cyclooctene) in different solvents yielded complexes of all three common oxidation states of rhodium, depending on the solvent used. When the reaction was carried out in methanol a cyclometalated, solvent-stabilized RhIIIalkylhydride complex (2) was obtained. However, when the reaction was carried out in acetone or dichloromethane a dinuclear η6-arene RhII complex (5) was obtained in the absence of addedredox reagents. Moreover, when acetonitrile was added to a solution of either the RhII or Rh III complexes, a new solvent-stabilized, noncyclometalated Rh I complex (6) was obtained. In this report we describe the different complexes, which were fully characterized, and probe the processes behind the remarkable solvent effect observed.

KW - Arene complexes

KW - C-H activation

KW - Oxidation state

KW - Phosphanes

KW - Rhodium

KW - Solvent effects

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