Tuning the Reactivity of Dioxoruthenium(VI) Porphyrins toward an Arylimine by Altering Porphyrin Substituents

Huang, Jie‐Sheng; Leung, Sarana Ka-Yan; Zhou, Zhóngyuan; Zhu, Nianyong; Che, Chi‐Ming

doi:10.1021/ic0484102

Cited by 17 publications

(18 citation statements)

References 61 publications

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“…These geometric parameters are comparable to those of the linear arylimido complex [(h 6 -cymene)Ru = N-2,4,6-tBu 3 C 6 H 2 ] (Ru-N-C: 177.8(4)8; Ru-N(arylimido): 1.753 (3) ) [14] and linear methyleneamido complex (4) ). [12] The bond lengths and a angle shown in Figure 2 agree well with the quinoneimido core. The RuÀOEt distances of 1.92 (3) (1 a) and 1.914 (7) (1 b) fall within the range of 1.892 (3) [15a] and [Ru IV…”

Section: [Ru IV a C H T U N G T R E N N U N G (Por)a C H T U N G T R supporting

confidence: 54%

“…2 )(OH)] (419 and 527 nm). [12] The IR spectra of 2 a-c exhibit oxidation state marker bands [10a] at 1012-1015 cm À1 , consistent with a Ru IV formulation. [10a, 12] In the electrospray mass spectra of The X-ray crystal structures of 1 a·2EtOH and 1 b·1.5H 2 O were determined (Figure 2; see also Table S1 and Figures S5 and S6 in the Supporting Information).…”

mentioning

confidence: 72%

“…Owing to the unsymmetrical coordination of the axial sites, the H b and H b’ atoms of the meso ‐tolyl groups give different signals. The H a signal ( δ =8.71 ppm) of 2a appears at a lower field than those of [Ru IV (ttp)(NH‐ p ‐ClC 6 H 4 ) 2 ] ( δ =8.41 ppm10a) and methyleneamido complex [Ru IV (ttp)(N=CPh 2 )(OH)] ( δ =8.61 ppm12).…”

Section: Methodsmentioning

confidence: 99%

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Quinoneimido Complexes of a Metalloporphyrin: Isolation, X‐ray Crystal Structures, and DFT Calculations

Tsui

Huang

Tong

et al. 2010

Chemistry An Asian Journal

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Quinoneimine and quinoneimido ligands (designated here as QuNR and QuN À , respectively) bear close relevance to arylamido (ArNR À ) and arylimido (ArN 2À ) ligands (Scheme 1). [1] The latter two have been subjected to immense studies in the field of metal-ligand multiple-bonded complexes and in metal-catalyzed nitrogen/group-transfer catalysis. [2] While there are a large number of metal complexes of quinoneimines known in the literature, [3,4] quinoneimido complexes of transition metals are sparse. [5][6][7] In the early 1990s, Sharp and co-workers [5a,b] reported di-or tetranuclear rhodium complexes analogous to bridging quinoneimido complexes. Subsequently, bridging quinoneimido ligands were reported to exist in a few di-or trinuclear osmium [5c] and palladium/platinum [5d] complexes and hexanuclear osmium complexes, [5e] with the oxidation states of the metal ions being +2 or less. Terminal quinoneimido complexes of transition metals are extremely rare, which were once considered (as hypothetical species) in the oxidation of nickel o-phenylenediamine complexes [8] and were proposed to be the key intermediates in dirhodium-catalyzed carbazole formation from biaryl azides. [9] To the best of our knowledge, only one transition-metal complex bearing a terminal quinoneimido ligand has been isolated and reported in literature, that is, a mono(quinoneimido) nickel(II) complex recently reported by Stephan and Bai. [6] Herein we report the isolation, spectroscopy, and X-ray crystal structures of several terminal quinoneimido complexes of ruthenium(IV), which constitute the first quinoneimido complexes of a metalloporphyrin.Our approach to quinoneimido complexes came from an unexpected reaction of high-valent metal-oxo complexes [Ru VI A C H T U N G T R E N N U N G (por)O 2 ] (por = porphyrinato 2À ) with an aniline derivative, in contrast to the formation of the mono(quinoneimido) nickel(II) complex from reaction of a b-diketiminate nickel(II) complex with an aryl azide. [6] We previously reported that [Ru VI O 2 ] (por = ttp, [11a] 4-MeO-tpp, [11b] 4-Cl-tpp [11c] ) with 20 equiv of 2,6-dimethylaniline in ethanol for 8 h produced a red purple precipitate, which was found to be a mixture of quinoneimido complexes [Ru IV (OH)] (por = ttp: 2 a; 4-MeO-tpp: 2 b; 4-Cl-tpp: 2 c) (yield % 65 %). Complexes 2 probably resulted from the hydrolysis of 1 owing to the presence of a trace amount of water in the solvent. Indeed, stirring a mixture of [a] Dr.

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Section: [Ru IV a C H T U N G T R E N N U N G (Por)a C H T U N G T R supporting

confidence: 54%

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confidence: 72%

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Quinoneimido Complexes of a Metalloporphyrin: Isolation, X‐ray Crystal Structures, and DFT Calculations

Tsui

Huang

Tong

et al. 2010

Chemistry An Asian Journal

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“…After attachment to the metal‐oxide surface through a phosphonate linkage, the Ru II centers were oxidized, either chemically or electrochemically, to the highly reactive Ru VI ‐dioxo species trans ‐[(H 2 O 3 P‐tpy)Ru(O) 2 (H 2 O)] 2+ , which remained attached to the surface. The surface‐bound Ru VI complex reacted with benzylic alcohols by a similar mechanistic pathway as proposed for solution;144–149 the Ru VI state was reduced stepwise in two consecutive two‐electron transfer processes, via a Ru IV to a Ru II state. Reduction of the Ru VI center was accompanied by the insertion to the CH bond of benzyl alcohol, as the rate‐limiting step, to yield a coordinated aldehyde hydrate, which was subsequently solvolyzed to the aldehyde (Scheme ).…”

Section: Tri‐n‐oxides and Complexes Of 22′:6′2′′‐terpyridines As Camentioning

confidence: 86%

Catalytic Applications of Terpyridines and their Transition Metal Complexes

2011

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The coordination compounds of the tridentate oligopyridine ligand 2,2′:6′,2′′‐terpyridine (tpy) are utilized in very different fields of research, such as materials science (e.g. photovoltaics), biomedicinal chemistry (e.g. DNA intercalation), and organometallic catalysis. Applications in the latter area have arisen from initial reports on electro‐ or photochemical processes and, today, a broad range of reactions—from artificial photosynthesis (water splitting) to biochemical and organic transformations as well as polymerization reactions—have been catalyzed by terpyridines and their transition metal complexes. In this review, the scope and the limitations of these applications, which emerged particularly in organic and macromolecular chemistry, will be evaluated.

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“…The Ru-OH bond lengths [2.016(14) and 2.028(14) Å] are in accordance with the literature for Ru IV -OH-containing compounds. [52][53][54][55][56][57] Indeed the {Ru IV -H 2 O} bond lengths usually lie in the range 2.1 to 2.2 Å, [54,[58][59][60] although they are shorter [2.042(4) …”

Section: Introductionmentioning

confidence: 99%

Hydrothermal Synthesis and Structural Characterization of the High‐Valent Ruthenium‐Containing Polyoxoanion [{PW₁₁O₃₉}₂{(HO)Ru^IV–O–Ru^IV(OH)}]^10–

Chen

Villanneau

et al. 2008

Eur J Inorg Chem

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The high‐valent ruthenium‐containing [{PW11O39}2{(HO)RuIV–O–RuIV(OH)}]10– anion (1) has been synthesized by hydrothermal reaction and characterized by X‐ray diffraction, IR, multinuclear (31P and 183W) NMR spectroscopy andelectrochemistry. Single‐crystal analysis was carried outon Rb10[{PW11O39}2{(HO)RuIV–O–RuIV(OH)}]·21H2O, which crystallizes in the monoclinic system, space group P21/n, with a = 11.1912(14), b = 21.9257(12), c = 38.7310(96) Å, β = 94.682(19)°, V = 9472(3) Å3, Z = 4. Polyanion 1 consists of two lacunary [α‐PW11O39]7– anions connected by a linear {(HO)Ru–O–Ru(OH)}4+ unit. Each ruthenium ion achieves six‐coordination through interaction with two terminal oxo ligands from the lacuna of each [PW11O39]7– anion.(© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2008)

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Tuning the Reactivity of Dioxoruthenium(VI) Porphyrins toward an Arylimine by Altering Porphyrin Substituents

Cited by 17 publications

References 61 publications

Quinoneimido Complexes of a Metalloporphyrin: Isolation, X‐ray Crystal Structures, and DFT Calculations

Quinoneimido Complexes of a Metalloporphyrin: Isolation, X‐ray Crystal Structures, and DFT Calculations

Catalytic Applications of Terpyridines and their Transition Metal Complexes

Hydrothermal Synthesis and Structural Characterization of the High‐Valent Ruthenium‐Containing Polyoxoanion [{PW₁₁O₃₉}₂{(HO)Ru^IV–O–Ru^IV(OH)}]^10–

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Tuning the Reactivity of Dioxoruthenium(VI) Porphyrins toward an Arylimine by Altering Porphyrin Substituents

Cited by 17 publications

References 61 publications

Quinoneimido Complexes of a Metalloporphyrin: Isolation, X‐ray Crystal Structures, and DFT Calculations

Quinoneimido Complexes of a Metalloporphyrin: Isolation, X‐ray Crystal Structures, and DFT Calculations

Catalytic Applications of Terpyridines and their Transition Metal Complexes

Hydrothermal Synthesis and Structural Characterization of the High‐Valent Ruthenium‐Containing Polyoxoanion [{PW11O39}2{(HO)RuIV–O–RuIV(OH)}]10–

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Product

Resources

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Hydrothermal Synthesis and Structural Characterization of the High‐Valent Ruthenium‐Containing Polyoxoanion [{PW₁₁O₃₉}₂{(HO)Ru^IV–O–Ru^IV(OH)}]^10–