Rearrangement of 3-Rhoda-1,2-dioxolanes to Rhodium Formylmethyl Hydroxy Complexes

Krom, Monique; Coumans, Ruud G. E.; Smits, J.M.; Gal, Anton W.

doi:10.1002/1521-3773(20020215)41:4<575::aid-anie575>3.0.co;2-e

Cited by 20 publications

(11 citation statements)

References 16 publications

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“…17,18 This mechanism is consistent with literature mechanisms 9,14,15 for the decay of (alkene)peroxo complexes and with experimental examples of rearrangement of 3-metalla-1,2-dioxolanes into β-oxoalkyl complexes. 7,51 Loss of H 2 O or OH − from [Ir(L)(η 2 -C 8 H 11 O-κC)(OH)] would then give rise to {3 − H 2 O} or {3 − OH} + , respectively. Also observed was a peak consistent with {3 − O 2 H} + (Table S7 †), which may be attributed to an (η 5 -cycloocta-2,5dien-1-yl) complex, [Ir(L)(η 5 -C 8 H 11 )] + .…”

Section: Reactivity Of [Ir{phnc(me)nph}(cod)(o 2 )]mentioning

confidence: 99%

“…Alkene oxygenation has only been reported for [IrCl(PPh 3 ) 2 (C 2 H 4 )(O 2 )] under concomitant oxygenation of PPh 3 . 16 Relevant precedents for the decay products of 3 and 4 include an (oxo-η 2 -cyclooctenyl) complex of Ir, 56 prepared using H 2 O 2 , and 2-oxoethyl complexes of Rh and Ir, 7,51 prepared using O 2 .…”

Section: Formation and Reactivity Of The (Alkene)peroxoiridium(iii) I...mentioning

confidence: 99%

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Formation and reactivity of an (alkene)peroxoiridium(iii) intermediate supported by an amidinato ligand

Kelley

Rohde

2014

Dalton Trans.

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An Ir(I) complex of an acetamidinato ligand was synthesized by reaction of N,N'-diphenylacetamidine, PhN[double bond, length as m-dash]C(Me)NHPh, with either MeLi and [{Ir(cod)}2(μ-Cl)2] or [{Ir(cod)}2(μ-OMe)2] and was characterized by X-ray crystallography as a mononuclear complex, [Ir{PhNC(Me)NPh}(cod)] (1; where cod = 1,5-cyclooctadiene). Reaction of 1 with CO afforded a dinuclear carbonyl complex, [{Ir(CO)2}2{μ-PhNC(Me)NPh-κN:κN'}2] (2), as indicated by EI mass spectrometry and solution- and solid-state IR spectroscopy [νCO (n-pentane) = 2067, 2034 and 1992 cm(-1)]. Activation of O2 by 1 in solution at 20 °C was irreversible and produced an (alkene)peroxoiridium(iii) intermediate, [Ir{PhNC(Me)NPh}(cod)(O2)] (3), which was characterized by one- and two-dimensional NMR techniques and IR spectroscopy (for 3, νOO = 860 cm(-1); for 3-(18)O2, νOO = 807 cm(-1)). Complex 3 oxidized PPh3 to OPPh3, and its decay in the absence of added substrates followed by reaction with cod yielded 4-cycloocten-1-one and a minor amount of 1. In comparison with the results for the previously reported guanidinato complex [Ir{PhNC(NMe2)NPh}(cod)(O2)] (4), the formation of 3 and its reaction with PPh3 are significantly faster, indicating considerable ligand effects in these reactions.

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Section: Reactivity Of [Ir{phnc(me)nph}(cod)(o 2 )]mentioning

confidence: 99%

Section: Formation and Reactivity Of The (Alkene)peroxoiridium(iii) I...mentioning

confidence: 99%

Formation and reactivity of an (alkene)peroxoiridium(iii) intermediate supported by an amidinato ligand

Kelley

Rohde

2014

Dalton Trans.

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“…From a mechanistic point of view, radical chain processes have been proposed in some instances, but Scheme suggests two main routes that can be related with the number of oxygen atoms remaining in the products. In the upper part of the Scheme , after activation of dioxygen to render (alkene)(peroxo) species, the C−O bond formation seems to be a consequence of alkene insertion into the M−O bond while the cleavage of the O−O bond requires an active β‐hydrogen . Such type of reactivity is not exclusive of olefins and has been also observed in the oxygenation of bis(picolyl)imine .…”

Section: Introductionmentioning

confidence: 91%

“…For the less studied rhodium and iridium ethylene complexes bearing the tetrapodal tris‐(2‐pyridylmethyl)amine ligand, 3‐metalla‐1,2‐dioxolanes were prepared from solid–gas reactions with dioxygen . They were found to be highly reactive species evolving to the corresponding (hydroxo)(formylmethyl) complexes upon exposure to light . In sharp contrast, related complexes with tris‐(6‐methyl‐2‐pyridylmethyl)amine produce remarkably stable (ethylene)(peroxo) compounds, in which C−O bond formation does not occur…”

Section: Introductionmentioning

confidence: 99%

Rhodium Complexes Promoting C−O Bond Formation in Reactions with Oxygen: The Role of Superoxo Species

Vilella-Arribas

García‐Melchor

Balcells

et al. 2017

Chemistry A European J

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C-O bond formation in reactions of olefins with oxygen is a long standing challenge in chemistry for which the very complicated-sometimes controversial-mechanistic panorama slows down the design of catalysts for oxygenations. In this regard, the mechanistic details of the oxidation of the complex [Rh(cod)(Ph N )] (1) (cod=1,5-cyclooctadiene) with oxygen to the unique 2-rhodaoxetane compound [{Rh(OC H )(Ph N )} ] (2) has been investigated by DFT calculations. The results of this study provide evidences for a novel bimetallic mechanism in which two rhodium atoms redistribute the four electrons involved in the cleavage of the O=O bond. Furthermore, both oxygen atoms are used to create two new C-O bonds in a controlled fashion with 100 % atom economy. The key intermediates that we have found in this process are a mononuclear open-shell triplet superoxo compound, an open-shell singlet "μ-(peroxo)" derivative, and a closed-shell singlet "bis(μ-oxo)" complex. Some of the findings are used to predict the reactions of Rh complexes with oxygen, exemplified by that of the complex [Rh(cod)(OnapyMe )] (3). Starting from 3, [{Rh(OC H )(OnapyMe )} ] (4) has been prepared and characterized, which represents the second example of a 2-rhodaoxetane compound coming from an oxygenation reaction with oxygen.

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“…Various reactions and complexes that may serve as models for the steps and intermediates in the Wacker reaction have appeared in the literature. − Some time ago we reported stoichiometric ethylene oxidation to acetaldehyde by Pt(II) oxo complex 1 and formation of platinaoxetane 3 from the reaction of the strained alkene norbornene (NB) with 1 (Scheme ) and suggested this system as a model for 1,2-addition in Wacker alkene oxidation. , Since then we have traced the reactivity of oxo complex 1 to hydroxo complex [Pt(COD)(μ-OH)] 2 (OTf) 2 ( 4 ) , and reported the proton-catalyzed reaction of 4 with NB (Scheme ). , The 1,2-addition of NB to the Pt–OH bond of 4 is rapid and reversible. (For other alkene 1,2-additions to Pt–OH bonds see refs and .)…”

Section: Introductionmentioning

confidence: 99%

Ethylene Oxidation by a Platinum(II) Hydroxo Complex. Insights into the Wacker Process

Weliange

Sharp

2012

Organometallics

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The ethylene reaction of hydroxo complex [Pt(COD)(μ-OH)] 2 (OTf) 2 (4) yields acetaldehyde and an equilibrium mixture of Pt 11) are detected as intermediates during the reaction. The reaction displays three phases:(1) an induction period, (2) an accelerating reaction yielding intermediate 11, water, and 6 plus 7, and (3) a linear decrease in the concentration of 11 with simultaneous formation of acetaldehyde and more 6 plus 7. The reaction is proton catalyzed, and phases 1 and 2 are attributed to autocatalytic behavior resulting from the acidic complex of 6 with water, [Pt(COD)(C 2 H 5 )(OH 2 )]OTf. Phase 3 is initiated by the complete consumption of basic 4 and the resulting release of protons to catalyze the reaction of 11 with water and ethylene to give acetaldehyde and 6 plus 7.

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Rearrangement of 3-Rhoda-1,2-dioxolanes to Rhodium Formylmethyl Hydroxy Complexes

Cited by 20 publications

References 16 publications

Formation and reactivity of an (alkene)peroxoiridium(iii) intermediate supported by an amidinato ligand

Formation and reactivity of an (alkene)peroxoiridium(iii) intermediate supported by an amidinato ligand

Rhodium Complexes Promoting C−O Bond Formation in Reactions with Oxygen: The Role of Superoxo Species

Ethylene Oxidation by a Platinum(II) Hydroxo Complex. Insights into the Wacker Process

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