Reactions of functionalised aryl groups σ-bound to ruthenium(II)

Clark, George R.; Rickard, Clifton E. F.; Roper, Warren R.; Wright, L. James; Patricia, V.; Yap, Dahrika M. L.

doi:10.1016/s0020-1693(96)05253-x

Cited by 18 publications

(8 citation statements)

References 26 publications

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“…Electrophilic substitution at the para and ortho positions of aryl units substituted by ruthenium was investigated first by Roper et al148 These authors found that the aryl–Ru bond was very much resistant towards electrophilic substitution reaction conditions, as the aryl rings σ‐bonded to ruthenium could be nitrated in the presence of Cu(NO 3 ) 2 and acetic anhydride without affecting the Ru–C bond. Moreover, the resulting 4‐nitrophenyl ligand could be reduced with zinc and HCl to afford a 4‐aminoarylruthenium complex that could be acetylated to the corresponding amide, which demonstrates the great robustness of the Ru–C bond 149. Cycloruthenated phenylpyridine is more prone to be nitrated than free 2‐phenylpyridine, as ortho and para substitutions of the phenyl group were found to take place in presence of an excess of copper nitrate in acetic anhydride, however in low yield (Scheme ).…”

Section: Reactivity Of the Cycloruthenated Unitmentioning

confidence: 99%

Cycloruthenated Compounds – Synthesis and Applications

et al. 2009

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The syntheses of cycloruthenated compounds by several methods, and especially by the C-H activation pathway, have been reviewed. Many ruthenium-containing starting materials lead to these interesting organometallic compounds, which have found various applications in different fields of chemistry. Their reactivity highlights both the variety of reactions that were found to occur at the Ru-C bonds as well as the inertness of the organometallic moiety when these species are exposed to strongly oxidizing molecules or to reactive halogenation reagents. Their use as catalyst precursors showed them to be particularly efficient for hydrogenation reactions, either by H 2 or by hydride transfer.

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Section: Reactivity Of the Cycloruthenated Unitmentioning

confidence: 99%

Cycloruthenated Compounds – Synthesis and Applications

et al. 2009

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“…Other methods using organolithium or tin derivatives, oxidative-addition reactions, − arylhydrazonium salts, or direct metalation of arenes − have more limited applicability. Recently, even the nitration of aryl complexes has been reported. , Our interest in the synthesis of nitroaryl complexes is based on the great stability of these complexes (allowing, for example, the synthesis of carbonyl arylpalladium(II) complexes 70 ) and on the study of the structural properties and the coordination ability of the nitro group. We have shown, for example, that the −I rather than −M effect is observable in most nitroaryl complexes, according to their structures. ,,,− We have studied complexes containing 2-nitro- and 2,4,6-trinitroaryl ligands and shown that, while for the former case the aryl ligand can be mono- or dicoordinated, for the latter the ligand 68-70 can only be monocoordinated.…”

Section: Introductionmentioning

confidence: 99%

Attempts To Prepare Palladium(II) Complexes with the O,C,O Pincer Aryl Ligand C₆(NO₂)₂-2,6-(OMe)₃-3,4,5

et al. 1998

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The complex [HgR2] (R = C6(NO2)2-2,6-(OMe)3-3,4,5-C1 (2)), obtained by thermal decomposition of [Hg(O2CR)2] (1), reacts with Q2[Pd2Cl4(μ-Cl)2] to give [Hg(R)Cl] (3) and Q2[Pd(R)Cl(μ-Cl)]2 (Q = (PhCH2)Ph3P (4a), Me4N (4b)), which react (i) with Tl(acac) (1:2, acac = acetylacetonate) to give Q[Pd(R)Cl(O,O-acac)] (Q = (PhCH2)Ph3P (5a), Me4N (5b)) or (ii) with AgClO4 (1:2) to give [Pd(κ3-R)Cl] (κ3-R = κ3-C6(NO2)2-2,6-(OMe)3-3,4,5-C1,O,O‘ (6)), which can also be obtained by reacting 5a with HBF4. Complex 6 reacts with p-toluidine (1:1, L) to give [Pd(R)(μ-Cl)L]2 (7). Complex 5b decomposes in a mixture of acetone/water to give [Pd(κ2-R)(O,O-acac)] (κ2-R = κ2-C6(NO2)2-2,6-(OMe)3-3,4,5-C1,O (8)), which reacts (i) with neutral monodentate ligands to give [Pd(R)(O,O-acac)L] (L = PPh3 (9), pyridine (py) (10), tetrahydrothiophene (11)), (ii) with bis(diphenylphosphino)methane (dppm) to give a complex that readily oxidizes to give [Pd(R)(O,O-acac)(dppmO)] (dppmO = monoxide of bis(diphenylphosphino)methane (12)), (iii) with 1,10-phenanthroline (phen) to give [Pd(R)(C-acac)(phen)] (13), and (iv) with protonated ligands (HL)ClO4 to give 10 (L = py) or cis-[Pd(R)(H2O)2(PPh3)]·H2O (L = PPh3 (14)). Trifluoromethanesulfonic acid (HOSO2CF3) reacts with 9 and PPh3 or with 13 to give trans-[Pd(R)(OSO2CF3)(PPh3)2] (15) or [Pd(R)(OSO2CF3)(phen)] (16), respectively. The X-ray crystal structures of 7·2CH 2 Cl 2 , 8, 10, and 14·H 2 O have been determined.

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“…The latter complex could be acetylated to the corresponding amide, [25] again highlighting the stability of the RuÀC aryl s bond.…”

Section: Angewandte Chemiementioning

confidence: 86%

“…Treatment of 23 a with nBuLi gave intermediate 24, which underwent further reactions typical of aryllithium reagents (Scheme 6). [30] This constitutes a valuable route to the introduction of a wide range of functional groups (see complexes [25][26][27].…”

Section: Regioselective Electrophilic Substitution Of Heterocyclic Pomentioning

confidence: 99%

Organic Transformations on σ‐Aryl Organometallic Complexes

et al. 2007

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This work reviews recent developments in the field of organic transformations on sigma-aryl organometallic complexes. The general notion that M--C sigma bonds are kinetically labile, highly reactive, and incompatible with typical reaction conditions met in organic synthesis has limited the use of these synthetic strategies thus far. However, organic transformations on metal-bound sigma-aryl fragments are being used more and more by chemists in both industry and academia. In this Review, emphasis is put on the synthetic methods applied in this field up to now. The simplicity and generally good yields of these methods are very attractive for the construction of functionalized organometallic building blocks that are potentially useful as photochemical molecular devices, biosensors and -conjugates, or molecular switches. Thus, this Review has been tailored for a broader audience with the aim of encouraging the application of these strategies.

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Reactions of functionalised aryl groups σ-bound to ruthenium(II)

Cited by 18 publications

References 26 publications

Cycloruthenated Compounds – Synthesis and Applications

Cycloruthenated Compounds – Synthesis and Applications

Attempts To Prepare Palladium(II) Complexes with the O,C,O Pincer Aryl Ligand C₆(NO₂)₂-2,6-(OMe)₃-3,4,5

Organic Transformations on σ‐Aryl Organometallic Complexes

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Reactions of functionalised aryl groups σ-bound to ruthenium(II)

Cited by 18 publications

References 26 publications

Cycloruthenated Compounds – Synthesis and Applications

Cycloruthenated Compounds – Synthesis and Applications

Attempts To Prepare Palladium(II) Complexes with the O,C,O Pincer Aryl Ligand C6(NO2)2-2,6-(OMe)3-3,4,5

Organic Transformations on σ‐Aryl Organometallic Complexes

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Attempts To Prepare Palladium(II) Complexes with the O,C,O Pincer Aryl Ligand C₆(NO₂)₂-2,6-(OMe)₃-3,4,5