Reactions of benzene based half sandwich ruthenium(II) complex with 2,6-bis((phenylseleno)methyl)pyridine: Preferential substitution of ring resulting in a catalyst of high activity for oxidation of alcohols

Das, Dipanwita; Singh, Pradhumn; Prakash, Om; Singh, Ajai K.

doi:10.1016/j.inoche.2010.07.039

Cited by 13 publications

(4 citation statements)

References 46 publications

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“…70 pyridine (L7) is the only pincer ligand whose Ru(II) complex is explored as catalyst. 100 The commonly used sources of ruthenium for designing half sandwich ruthenium complexes of Chart 8 are [{(η 6 -C 6 H 6 )RuCl(μ-Cl)} 2 ] and [{(η 6 -p-cymene)-RuCl(μ-Cl)} 2 ]. These precursors are commercially available and can also be easily synthesized by literature methods.…”

Section: Ruthenium(ii) Complexesmentioning

confidence: 99%

Organoselenium ligands in catalysis

et al. 2012

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Organoselenium ligands are building blocks of several transition metal complexes which catalyze various organic reactions efficiently in solution. In this review the survey of developments pertaining to the designing of such complexes (along with their Se-ligands), and their uses as catalysts for various organic reactions has been presented with critical analysis of present status of the subject. Undoubtedly a new family of catalysts or their precursors has been generated by organoselenium ligands. The catalytic activity and selectivity of their metal complexes can sometimes be fine-tuned efficiently by changing the ligand's framework. They show good thermal and air-stability. This, coupled with ease in their handling and synthesis, may make them not only attractive but good alternatives to several popular catalysts.

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Section: Ruthenium(ii) Complexesmentioning

confidence: 99%

Organoselenium ligands in catalysis

et al. 2012

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“…The reactivity of 1 and 2 towards PEt 3 , ethene and DMSO has been examined. Thermally, for the reaction with PEt 3 , the bissubstituted products CpRu(PEt 3 ) 2 Cl (4) and CpRu(PEt 3 ) 2 Me (7) are readily formed via their mono-substituted counterparts CpRu(PPh 3 )(PEt 3 )Cl (5) and CpRu(PPh 3 )(PEt 3 )Me ( 8). In contrast, under broad-band UV irradiation, 1 and 2 react to selectively produce 5 and 8.…”

Section: Discussionmentioning

confidence: 99%

“…Over the last half century, this class of complex has been used to study the activation of small molecules and to facilitate a number of catalytic transformations. [6][7][8][9] Studies of the thermal reactivity of CpRu(PPh 3 ) 2 Me (2) have demonstrated that it is more reactive than 1, undergoing intramolecular C-H bond activation at 363 K in decalin to form the orthometallation product CpRu(κ 2 -2-C 6 H 4 PPh 2 )(PPh 3 ) (3). 10,11 Similarly, the C-H bond activation of benzene by 2 or 3 produces CpRu(PPh 3 ) 2 Ph while toluene leads to CpRu(PPh 3 ) 2 (CH 2 C 6 H 5 ) and meta and para tolyl derivatives CpRu(PPh 3 ) 2 (C 6 H 4 Me).…”

Section: Introductionmentioning

confidence: 99%

Photochemical studies of (η⁵-C₅H₅)Ru(PPh₃)₂Cl and (η⁵-C₅H₅)Ru(PPh₃)₂Me: formation of Si–H and C–H bond activation products

Clark

Duckett

2014

Dalton Trans.

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Studies examining the photochemical reactivity of CpRu(PPh3)2Cl and CpRu(PPh3)2Me towards the two electron donor ligands PEt3, C2H4, DMSO, the CH bond activatable reagents tetrahydrofuran, toluene, and pyridine, and the SiH bond activatable reagents HSiEt3 and HSi(Me)2CH=CH2) are presented. Broadband UV irradiation of CpRu(PPh3)2Cl leads to the formation of mono-substitution products such as CpRu(PPh3)(PEt3)Cl which are inert to further photochemical reaction, although thermally bis-substituted products such as CpRu(PEt3)2Cl can be formed. Room temperature irradiation of the related complex CpRu(PPh3)2Me with L = PEt3, C2H4, and DMSO also produces CpRu(PPh3)(L)Me. However, when these reactions are followed by in situ laser irradiation (325 nm source) at low temperature, three solvent activated isomers (ortho, meta and para) of CpRu(PPh3)2(C6H4Me) are detected in toluene in addition to η(1)- and η(3)-coordinated benzyl species. Furthermore, photolysis in THF leads to both the C-D bond activation product CpRu(PPh3)2(OC4D7) and the labile coordination complex CpRu(PPh3)(THF)Me. Now CH4 rather than CH3D is liberated which suggests the involvement of an orthometallated species. The photochemically driven reaction of CpRu(PPh3)2Me with HSiEt3 at 198 K generates CpRu(κ(2)-2-C6H4PPh2)(SiEt3)H and thereby confirms a role for an orthometallated complex is this process. Irradiation in cyclohexane produces the known orthometallated complex, CpRu(κ(2)-2-C6H4PPh2)(PPh3), and CH4 in accordance with this reactivity.

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“…Transfer hydrogenation has emerged as a convenient and versatile method for the reduction of carbonyl compounds; it is an attractive alternative to hydrogenation because it is easy to execute due to the absence of hazardous hydrogen gas and pressure vessels to handle it . Transfer hydrogenation of ketones has been catalyzed by a number of ruthenium species, including half-sandwich complexes . However, Rh and Ir complexes, particularly half-sandwich types containing organochalcogen ligands, have scarcely been explored .…”

Section: Introductionmentioning

confidence: 99%

(η⁵-Cp*)Rh(III)/Ir(III) Complexes with Bis(chalcogenoethers) (E, E′ Ligands: E = S/Se; E′ = S/Se): Synthesis, Structure, and Applications in Catalytic Oppenauer-Type Oxidation and Transfer Hydrogenation

et al. 2014

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The air-and moisture-insensitive half-sandwich complexes [(η 5 -Cp*)Rh(L)Cl][PF 6 ] (1−3) and [(η 5 -Cp*)Ir(L)Cl][PF 6 ] (4−6) have been prepared by reacting L = L1−L3 (1,2-bis(phenylthio)ethane (L1), 1-(phenylseleno)-2-(phenylthio)ethane (L2) and 1,2-bis(phenylseleno)ethane (L3)) with [(η 5 -Cp*)RhCl(μ-Cl)] 2 and [(η 5 -Cp*)IrCl(μ-Cl)] 2 , respectively, at room temperature followed by treatment with NH 4 PF 6 . Their HR-MS and 1 H, 13 C{ 1 H}, and 77 Se{ 1 H} NMR spectra have authenticated them. The single-crystal structures of 1− 6 have been established by X-ray crystallography. Complexes 1−6 have been explored for catalytic Oppenauer-type oxidation of alcohols and transfer hydrogenation of ketones with 2-propanol. 3 and 6 were the most efficient in the two catalytic reactions (TON values up to 9.9 × 10 2 and 9.8 × 10 3 , respectively) and were therefore investigated in detail. 3 is the first example of a Rh(III) species explored for Oppenauer-type oxidation. The catalysis appears to be homogeneous. In transfer hydrogenation it appears that one of the catalytic species is without a Cp* ring. DFT calculations indicate higher reactivity for Rh complexes in comparison to Ir complexes. This order has also been found for the two catalytic reactions experimentally. The calculated bond lengths/angles by DFT are generally consistent with the experimental values.

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Reactions of benzene based half sandwich ruthenium(II) complex with 2,6-bis((phenylseleno)methyl)pyridine: Preferential substitution of ring resulting in a catalyst of high activity for oxidation of alcohols

Cited by 13 publications

References 46 publications

Organoselenium ligands in catalysis

Organoselenium ligands in catalysis

Photochemical studies of (η⁵-C₅H₅)Ru(PPh₃)₂Cl and (η⁵-C₅H₅)Ru(PPh₃)₂Me: formation of Si–H and C–H bond activation products

(η⁵-Cp*)Rh(III)/Ir(III) Complexes with Bis(chalcogenoethers) (E, E′ Ligands: E = S/Se; E′ = S/Se): Synthesis, Structure, and Applications in Catalytic Oppenauer-Type Oxidation and Transfer Hydrogenation

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Reactions of benzene based half sandwich ruthenium(II) complex with 2,6-bis((phenylseleno)methyl)pyridine: Preferential substitution of ring resulting in a catalyst of high activity for oxidation of alcohols

Cited by 13 publications

References 46 publications

Organoselenium ligands in catalysis

Organoselenium ligands in catalysis

Photochemical studies of (η5-C5H5)Ru(PPh3)2Cl and (η5-C5H5)Ru(PPh3)2Me: formation of Si–H and C–H bond activation products

(η5-Cp*)Rh(III)/Ir(III) Complexes with Bis(chalcogenoethers) (E, E′ Ligands: E = S/Se; E′ = S/Se): Synthesis, Structure, and Applications in Catalytic Oppenauer-Type Oxidation and Transfer Hydrogenation

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Photochemical studies of (η⁵-C₅H₅)Ru(PPh₃)₂Cl and (η⁵-C₅H₅)Ru(PPh₃)₂Me: formation of Si–H and C–H bond activation products

(η⁵-Cp*)Rh(III)/Ir(III) Complexes with Bis(chalcogenoethers) (E, E′ Ligands: E = S/Se; E′ = S/Se): Synthesis, Structure, and Applications in Catalytic Oppenauer-Type Oxidation and Transfer Hydrogenation