Arene transition-metal chemistry. 5. Arene ligand exchange and reactivity in .eta.6-arene iridium(I) complexes

Sievert, Allen C.; Muetterties, E. L.

doi:10.1021/ic50216a034

Cited by 68 publications

(29 citation statements)

References 6 publications

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“…The phenoxo oxygen atom, for instance, is seen to lose more electron density upon p coordination through the carbon atoms in 6 b than when directly coordinated to Rh in 6 c. The C7 atom, on the other hand, has practically the same charge in all noncoordinated benzo rings, but becomes significantly more positively charged upon p coordination, whereas the negative charge on atoms C3 to C6 increases as expected for the h 5 resonant form. In agreement with the reactivity expected for rhodium or iridium arene complexes, [12] the p-coordinated benzo ring in complexes 4 and 5 can be easily displaced by acetonitrile to yield complexes 6 and 7 and the corresponding rhodium or iridium cationic derivatives (Scheme 5). …”

Section: H T U N G T R E N N U N G (O 2 Bz)a C H T U N G T R E N N U supporting

confidence: 77%

Chelating Dialkoxide Titanium Complex: A Versatile Building Block for the Construction of Heterometallic Derivatives

Fandos

Hernández

Otero

et al. 2007

Chemistry A European J

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The heterometallic complex [TiCp*(O(2)Bz)(2)AlMe(2)] (2) has been synthesised by reaction of [TiCp*(O(2)Bz)(OBzOH)] (1) with AlMe(3) (Cp*=eta(5)-C(5)Me(5); Bz=benzyl). Complex 1 reacts with HOTf to yield the cationic derivative [TiCp*(OBzOH)(2)]OTf (3) (HOTf=HSO(3)CF(3)). Compound 3 reacts with [{M(mu-OH)(cod)}(2)] (M=Rh, Ir; cod=cyclooctadiene) to render the early-late heterometallic complexes [TiCp*(O(2)Bz)(2){M(cod)}(2)]OTf (M=Rh (4); Ir (5)). The molecular structure of complex 4 has been established by single-crystal X-ray diffraction studies.

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Section: H T U N G T R E N N U N G (O 2 Bz)a C H T U N G T R E N N U supporting

confidence: 77%

Chelating Dialkoxide Titanium Complex: A Versatile Building Block for the Construction of Heterometallic Derivatives

Fandos

Hernández

Otero

et al. 2007

Chemistry A European J

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“…This also 281 agrees with the experimental [55] and DFT data [56][57][58][59] for complexes of transition metals with polycyclic aromatic molecules; therefore, the OMG prefers to coordinate to the arene rings of highest electron density, that is, at the periphery of the ligand rather than at its center for most of the 286 polycyclic arenes, though a few exceptions exist. [60,61] Nevertheless, in real experimental conditions, the size of the graphenic material should be large enough for the number of peripheral rings to be smaller than the number of inner rings to make the probability of coordination to inner sites 291 much larger. It should also be noted that several oxygencontaining substituents (methoxy, hydroxy, carboxylic, peroxide, etc.)…”

Section: Stability Of the Chromium Complexesmentioning

confidence: 99%

Chromium Tricarbonyl and Chromium Benzene Complexes of Graphene, Their Properties, Stabilities, and Inter‐Ring Haptotropic Rearrangements – A DFT Investigation

et al. 2014

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The structures, electronic properties, stabilities, mechanisms, and activation barriers of the intramolecular inter‐ring haptotropic rearrangements (η6,η6‐IRHRs) of chromium tricarbonyl and chromium benzene complexes of graphene were modeled by DFT calculations. All of the above calculated characteristics are in good agreement with the experimental data for related complexes with ultralarge, large, and medium‐sized polyaromatic ligands (PALs). Generally η6,η6‐IRHRs between isomer complexes with organometallic groups (OMGs) in different positions in graphene ligand proceeds via η3‐transition states with activation barriers considerably lower (<25 kcal/mol) than those of the corresponding rearrangements in medium‐sized PALs (>30 kcal/mol). This could be explained by the reduction of electron density and the increase of electron mobility inside graphene molecules, which weaken metal–ligand bonds and facilitate rearrangements.

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“…[Ir(CO) 4 ] − (46) may be synthesized by the reduction of Ir 4 (CO) 12 (45) with sodium under an atmosphere of carbon monoxide. More vigorous reduction of (45) (52). In one reaction they find a nonanuclear cluster, [Ir 9 (CO) 20 ] 3− (53), as a by-product.…”

Section: Mononuclear Carbonyl Complexes (See Metal Carbonyls)mentioning

confidence: 98%

Iridium: Organometallic Chemistry

Merola¹

2005

Encyclopedia of Inorganic Chemistry

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The organometallic chemistry of iridium is reviewed. The general classes of complexes of iridium containing iridium to carbon bonds are surveyed. The preparations of iridium olefin complexes, iridium arene complexes, iridium carbonyl complexes, iridium cyclopentadienyl complexes, and other types of complexes are covered along with the use of those classes of compounds in preparing other organometallic iridium species. In addition, three areas in which organoiridium compounds find particular application are specifically reviewed: catalysis utilizing organometallic compounds of iridium, carbon–hydrogen (CH) bond activation chemistry with iridium, and hydrodesulfurization (HDS) studies using iridium. References to other reviews, to monographs, and to the primary literature are provided in all cases.

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Arene transition-metal chemistry. 5. Arene ligand exchange and reactivity in .eta.6-arene iridium(I) complexes

Cited by 68 publications

References 6 publications

Chelating Dialkoxide Titanium Complex: A Versatile Building Block for the Construction of Heterometallic Derivatives

Chelating Dialkoxide Titanium Complex: A Versatile Building Block for the Construction of Heterometallic Derivatives

Chromium Tricarbonyl and Chromium Benzene Complexes of Graphene, Their Properties, Stabilities, and Inter‐Ring Haptotropic Rearrangements – A DFT Investigation

Iridium: Organometallic Chemistry

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