Photochemical arene exchange in the naphthalene complex [CpRu(η6-C 10H8)]+

Karslyan, Eduard E.; Perekalin, Dmitry S.; Petrovskii, P. V.; Borisova, A. O.; Kudinov, Alexander R.

doi:10.1007/s11172-009-0059-6

Cited by 17 publications

(8 citation statements)

References 20 publications

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“…The structures of the arene complexes [CpRu(1,4‐Me 2 C 6 H 4 )][PF 6 ] ( 2b [PF 6 ]), [CpRu(2,2‐paracyclophane)][PF 6 ] ( 2g [PF 6 ]), [CpRu(C 6 H 5 COOH)][BF 4 ] ( 2l [BF 4 ]), and [CpRu(cymene)][BPh 4 ] ( 2n [BPh 4 ]) were established by X‐ray diffraction (Figures 1, 2, 3, and 4). The Ru ··· C 5 (plane) distances (1.807–1.817 Å) are similar for all the compounds and are close to that in the starting naphthalene cation 1 (1.811 Å) 10,14b. The Ru ··· C 6 (plane) distances in cations 2b , l , n are also similar (1.690–1.705 Å), being somewhat shorter than that in 1 (1.719 Å).…”

Section: Resultssupporting

confidence: 58%

Arene Exchange in the Ruthenium–Naphthalene Complex [CpRu(C₁₀H₈)]⁺

et al. 2011

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Substitution of the naphthalene ligand in [CpRu(C10H8)]+ (1; Cp = cyclopentadienyl ligand) by other arenes occurs upon heating or visible‐light irradiation and gives complexes [CpRu(arene)]+ [arene = C6HnMe6–n, C6H5OH, C6H5OMe, C6H4(OMe)2, indene, 2,2‐paracyclophane] in 70–90 % yield. The reaction rate increases with coordinating ability of the solvent, CH2Cl2 < THF/CH2Cl2 < Me2CO, and counterion, [B(3,5‐(CF3)2C6H3)4]– < PF6– < BF4– < CF3SO3–. Acceptor or bulky substituents in the incoming arene slow down the exchange. Complexes with acceptor arenes C6H5COMe, C6H5COOH, and C6H4(COOH)2 were obtained by the exchange reaction in water. Complexes [CpRu(η6‐cycloheptatriene)]+ and [CpRu(η6‐cyclooctatetraene)]+ were obtained by irradiation of 1 with the corresponding cyclic polyenes. A similar reaction with α‐phellandrene is accompanied by dehydrogenation to give [CpRu(cymene)]+. Cation 1 reacts with 2‐naphthoic acid anion to give the zwitterionic complexes [CpRu]+[C10H7COO]– in which the [CpRu]+ fragment coordinates either at the substituted or unsubstituted ring. Upon protonation and subsequent irradiation, both isomers convert into [CpRu(C10H7COOH)]+ in which the metal atom coordinates only to the unsubstituted ring. The structures of [CpRu(p‐xylene)][PF6], [CpRu(2,2‐paracyclophane)][PF6], [CpRu(C6H5COOH)][BF4], and [CpRu(cymene)][BPh4] were determined by X‐ray diffraction.

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Section: Resultssupporting

confidence: 58%

Arene Exchange in the Ruthenium–Naphthalene Complex [CpRu(C₁₀H₈)]⁺

et al. 2011

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“…However, for reasons not clearly under stood, even the occurrence of η 6 ,η 6 Inter HR in them was not described, although such processes are quite probable and, most likely, do occur. In addition, according to our theoretical density functional theory calculations, they can have activation energies much lower, that is, occur under milder conditions, than those characteristic of well studied chromium tricar bonyl complexes, for instance, in the case of compar atively recently synthesized η 6 naphthalene complexes of Fe [16] and Ru [17], including complexes of substi tuted naphthalenes.…”

Section: Introductionmentioning

confidence: 76%

A density functional study of intra- and interring haptotropic η2,η2 rearrangements in rhodium, ruthenium, and osmium naphthalene complexes

Oprunenko

Gloriozov

2012

Russ. J. Phys. Chem.

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The density functional theory method was used to perform quantum chemical modeling of the mechanisms of η 2 ,η 2 intraring (Intra HR) and η 2 ,η 2 interring (Inter HR) haptotropic rearrangements for η 2 complexes of naphthalene with rhodium, ruthenium, and osmium. The structure of transition states and intermediates was studied, and the energy parameters of haptotropic rearrangements in these complexes were determined. We used the PBE functional, the TZV2p three exponential basis set for valence electrons, and the SBK JC relativistic pseudopotential for core electrons. η 2 ,η 2 Intra HR was found to occur inside the aro matic ring of η 2 naphthalene complexes without going outside it through intermediates and transition states with η n structures (n = 1, 2). Inter HR occurred as metal replacements on the periphery of the naphthalene ligand through intermediates and transition states with η n structures (n = 1, 2, 3) from one ring into another. The calculated activation barriers for η 2 ,η 2 Intra HR and η 2 ,η 2 Inter HR in the complexes studied closely agree with their experimental values.

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“…Thus, naphthalene substitution in 2 by arenes, phosphines, acetonitrile, amines takes place under mild conditions and can be accelerated by visible light. [20,22,[25][26][27][28][29][30][31][32] The microwave-mediated substitution of Cp for an arene ligand was extended to the preparation of a number of CpRu(arene) + complexes (Scheme 3).…”

Section: Resultsmentioning

confidence: 99%

“…(5). [29,44] (6). [20,28,44] [Ru(η 5 -Cp)(η 6 -pyrene)][PF 6 ] (11) [45] : 1 mmol scale, yield 0.429 g, 84 %.…”

Section: [Ru(η 5 -Cp)(η 6 -Naphthalene)][pf 6 ]mentioning

confidence: 99%

Microwave‐Assisted Synthesis and Transformations of Cationic CpRu(II)(naphthalene) and CpRu(II)(naphthoquinone) Complexes

Bocekova‐Gajdošíkova

Epik

Chou

et al. 2019

Helvetica Chimica Acta

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Details of the direct synthesis of cationic Ru(II)(η5‐Cp)(η6‐arene) complexes from ruthenocene using microwave heating are reported. Developed for the important catalyst precursor [Ru(II)(η5‐Cp)(η6‐1‐4,4a,8a‐naphthalene)][PF6] reaction time could be shortened from three days to 15 min. The method was extended to [Ru(II)(η6‐benzene)(η5‐Cp)][PF6], [Ru(II)(η5‐Cp)(η6‐toluene)][PF6], [Ru(II)(η5‐Cp)(η6‐mesitylene)][PF6], [Ru(II)(η5‐Cp)(η6‐hexamethylbenzene)][PF6], [Ru(II)(η5Cp)(η6‐indane)][PF6], [Ru(II)(η5‐Cp)(η6‐2,6‐dimethylnaphthalene)][PF6], and [Ru(II)(η5‐Cp)(η6‐pyrene)][PF6]. 1‐methylnaphthalene and 2,3‐dimethylnaphthalene afforded mixtures of regioisomeric complexes. [Ru(Cp)(CH3CN)3][PF6], derived from the naphthalene precursor provided access to the cationic RuCp complexes of naphthoquinone, tetralindione, 1,4‐dihydroxynaphthalene, and 1,4‐dimethoxynaphthalene. Reduction of the tetralindione complex afforded selectively the endo,endo diol derivative. X‐Ray structures of five complexes are reported.

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Photochemical arene exchange in the naphthalene complex [CpRu(η6-C 10H8)]+

Cited by 17 publications

References 20 publications

Arene Exchange in the Ruthenium–Naphthalene Complex [CpRu(C₁₀H₈)]⁺

Arene Exchange in the Ruthenium–Naphthalene Complex [CpRu(C₁₀H₈)]⁺

A density functional study of intra- and interring haptotropic η2,η2 rearrangements in rhodium, ruthenium, and osmium naphthalene complexes

Microwave‐Assisted Synthesis and Transformations of Cationic CpRu(II)(naphthalene) and CpRu(II)(naphthoquinone) Complexes

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Photochemical arene exchange in the naphthalene complex [CpRu(η6-C 10H8)]+

Cited by 17 publications

References 20 publications

Arene Exchange in the Ruthenium–Naphthalene Complex [CpRu(C10H8)]+

Arene Exchange in the Ruthenium–Naphthalene Complex [CpRu(C10H8)]+

A density functional study of intra- and interring haptotropic η2,η2 rearrangements in rhodium, ruthenium, and osmium naphthalene complexes

Microwave‐Assisted Synthesis and Transformations of Cationic CpRu(II)(naphthalene) and CpRu(II)(naphthoquinone) Complexes

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Arene Exchange in the Ruthenium–Naphthalene Complex [CpRu(C₁₀H₈)]⁺

Arene Exchange in the Ruthenium–Naphthalene Complex [CpRu(C₁₀H₈)]⁺