Crystal and molecular structure of bis(chloro(dioxygen)bis(triphenylphosphine)rhodium(I))

Bennett, Michael J.; Donaldson, Peter B.

doi:10.1021/ic50173a003

Cited by 58 publications

(26 citation statements)

References 32 publications

(1 reference statement)

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“…, the m-h 2 :h 1 -coordination mode is relatively common, having been characterised in complexes of W, [31] Mo, [32] V [33] and Rh, [34] for example. A m-h 2 :h 2 -coordination mode has also been characterised for the peroxo ligand in three copper(ii) complexes synthesised as models for the Cu 2 (m-h 2 :h 2 -O 2 ) centres in oxyhemocyanin and oxytyrosinase.…”

Section: Resultsmentioning

confidence: 99%

The First Structural Characterisation of a Group 2 Metal Alkylperoxide Complex: Comments on the Cleavage of Dioxygen by Magnesium Alkyl Complexes

Bailey

Coxall

Dick

et al. 2003

Chemistry A European J

149

164

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A new high-yield synthesis of [(PhCH(2))(2)Mg(thf)(2)] and [[(PhCH(2))CH(3)Mg(thf)](2)] via benzylpotassium has allowed a simple entry into benzylmagnesium coordination chemistry. The syntheses and X-ray crystal structures of both [(eta(2)-Me(2)NCH(2)CH(2)NMe(2))Mg(CH(2)Ph)(2)] and [eta(2)-HC[C(CH(3))NAr'](2)Mg(CH(2)Ph)(thf)] (Ar'=2,6-diisopropylphenyl) are reported. The latter beta-diketiminate complex reacts with dioxygen to provide a 1:2 mixture of dimeric benzylperoxo and benzyloxo complexes. The benzylperoxo complex [[eta(2)-HC[C(CH(3))NAr'](2)Mg(mu-eta(2):eta(1)-OOCH(2)Ph)](2)] is the first example of a structurally characterised Group 2 metal-alkylperoxo complex and contains the benzylperoxo ligands in an unusual mu-eta(2):eta(1)-coordination mode, linking the two five-coordinate magnesium centres. The O[bond]O separation in the benzylperoxo ligands is 1.44(2) A. Reaction of the benzylperoxo/benzyloxo complex mixture with further [eta(2)-HC[C(CH(3))NAr'](2)Mg(CH(2)Ph)(thf)] results in complete conversion of the benzylperoxo species into the benzyloxo complex. This reaction, therefore, establishes the cleavage of dioxygen by this system as a two-step process that involves initial oxygen insertion into the Mg[bond]CH(2)Ph bond followed by O[bond]O/Mg[bond]C sigma-bond metathesis of the resulting benzylperoxo ligand with a second Mg[bond]CH(2)Ph bond. The formation of a 1:2 mixture of the benzylperoxo and benzyloxo species indicates that the rate of the insertion is faster than that of the metathesis, and this is shown to be consistent with a radical mechanism for the insertion process.

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Section: Resultsmentioning

confidence: 99%

The First Structural Characterisation of a Group 2 Metal Alkylperoxide Complex: Comments on the Cleavage of Dioxygen by Magnesium Alkyl Complexes

Bailey

Coxall

Dick

et al. 2003

Chemistry A European J

149

164

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“…In the Rh(h 2 -O 2 ) moiety, the peroxido ligand is noticeably nonsymmetric (Rh(1)ÀO(2) 2.013(2), Rh(1)ÀO (1) 2.151(2) ), whereby the longer distance corresponds to the bridging oxygen atom, which in turn is closer to the other rhodium atom (Rh(1') À O (1) [12] and the recently described…”

mentioning

confidence: 79%

“…The O(1) À O(2) bond length of 1.463 (3) is in the range of O À O single bonds. Two precedents of this unusual bridging mode of a peroxido ligand have been reported to date for late transition metals: the related complex [{Rh(Cl)(PPh 3 ) 2 } 2 (mk 1 :h 2 -O 2 ) 2 ], [12] and the recently described [{Pd(k 2 -Tp iPr )} 2 (mk 1 :h 2 -O 2 )(py)] (Tp iPr = hydridotris(3,5-diisopropylpyrazolyl)borato). [8d] The dinuclear nature of 1 is maintained in solution according to NMR diffusion (DOSY) experiments.…”

mentioning

confidence: 96%

Stabilization of the Hydroperoxido Ligand: A 1κO,2κO′ Dimetallic Coordination Mode

Tejel

Ciriano²,

Jiménez³

et al. 2008

Angew Chem Int Ed

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A novel coordination mode of the hydroperoxido ligand in which each oxygen atom is bonded to a distinct metal center is present in a rare thermally stable example of this otherwise elusive family of complexes, which was obtained by protonating a bis‐peroxido‐bridged Rh2 complex. The OOH ligand is displaced by a chloride ion to give the corresponding chlorido‐bridged complex (see scheme, L3=tris(methylenediphenylphosphane)phenylborate).

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“…xv This binding mode has been observed more recently in dinuclear O 2 complexes of cobalt and rhodium. xvi Palladium complexes of this type have also been characterized. xvii In bioinorganic chemistry, μ-η 1 :η 2 -O 2 has been observed in a bimetallic iron-copper complex of relevance to cytochrome c oxidase, xviii and in dicopper complexes with asymmetric binucleating ligands.…”

Section: Binding Modesmentioning

confidence: 99%

Metal–dioxygen and metal–dinitrogen complexes: where are the electrons?

2010

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Transition-metal complexes of O2 and N2 play an important role in the environment, chemical industry, and metalloenzymes. This Perspective compares and contrasts the binding modes, reduction levels, and electronic influences on the nature of the bound O2 or N2 group in these complexes. The charge distribution between the metal and the diatomic ligand is variable, and different models for describing the adducts have evolved. In some cases, single resonance structures (e.g. M-superoxide = M–O2−) are accurate descriptions of the adducts. Recent studies have shown that the magnetic coupling in certain N22− complexes differs between resonance forms, and can be used to distinguish experimentally between resonance structures. On the other hand, many O2 and N2 complexes cannot be described well with a simple valence-bond model. Defining the situations where ambiguities occur is a fertile area for continued study.

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Crystal and molecular structure of bis(chloro(dioxygen)bis(triphenylphosphine)rhodium(I))

Cited by 58 publications

References 32 publications

The First Structural Characterisation of a Group 2 Metal Alkylperoxide Complex: Comments on the Cleavage of Dioxygen by Magnesium Alkyl Complexes

The First Structural Characterisation of a Group 2 Metal Alkylperoxide Complex: Comments on the Cleavage of Dioxygen by Magnesium Alkyl Complexes

Stabilization of the Hydroperoxido Ligand: A 1κO,2κO′ Dimetallic Coordination Mode

Metal–dioxygen and metal–dinitrogen complexes: where are the electrons?

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