Reactions of [Cp*RuOMe]2. 7. Intramolecular transformation of a RuOCH3 unit into a Ru(CO)H unit: crystal and molecular structure of Cp*Ru(.mu.-H)2(.mu.-CO)RuCp*

Kang, Byung Sun; Koelle, U.; Thewalt, Ulf

doi:10.1021/om00054a014

Cited by 26 publications

(12 citation statements)

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“…The five-membered ring seems to be planar, but this is most likely due to the disordered structure between the inversion isomers of the five-membered ring. Values of 2.048(6) Å for the Ru(1)–C(1) and Ru(2)–C(1) distances correspond to Ru–C single bonds and are similar to those of bridging alkylidene complexes of ruthenium. − The Ru(1)–Ru(2) distance of 2.4167(3) Å is similar to those observed in dinuclear ruthenium complexes with a 30-electron configuration containing two bridging hydrides, such as 1a (2.4630(5) Å), {Cp*Ru(μ-H)} 2 (μ-SiPh 2 ) (2.4683(5) Å), {Cp*Ru(μ-H)} 2 (μ-SiEtMe) (2.4492(9) Å), and {Cp*Ru(μ-H)} 2 (μ-CO) (2.444(1) Å) . Although hydrogen atoms directly bound to the ruthenium atoms were not located in the Fourier maps, they would be located in the space on the opposite side of the carbene ligand with respect to the Ru–Ru vector.…”

Section: Results and Discussionmentioning

confidence: 60%

Photoinduced Reactions of Diruthenium Tetrahydride Complexes: Carbon–Hydrogen Bond Cleavage of Tetrahydrofuran Leading to Bridging Cyclic Fischer-Type Carbene Complexes

Shimogawa¹,

Konishi²,

Takao

et al. 2016

Organometallics

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Photochemical reactions of diruthenium tetrahydride complexes containing cyclopentadienyls as auxiliary ligands, CpsRu(μ-H)4RuCps (1) (a: Cps = C5Me5 (Cp*), b: C5EtMe4 (CpEt), and c: 1,2,4-C5(t-Bu)3H2 (Cp‡)), with tetrahydrofuran were studied for elucidation of the reaction mode of dinuclear complexes containing multiple bridging hydrides. Complexes 1a–c reacted with tetrahydrofuran under UV irradiation (365 nm) to produce bridging cyclic Fischer-type carbene complexes, {CpsRu(μ-H)}2(μ-cyclo-CCH2CH2CH2O−)(μ-H)2 (5), via consecutive C–H bond cleavage at the α-position of the oxygen atom. The characteristic cyclic structures of the bridging carbene ligands were unambiguously confirmed by X-ray diffraction studies. Line-shape analysis of the variable-temperature 1H NMR spectra of 5c demonstrated the rotation of the bridging carbene ligand.

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Section: Results and Discussionmentioning

confidence: 60%

Photoinduced Reactions of Diruthenium Tetrahydride Complexes: Carbon–Hydrogen Bond Cleavage of Tetrahydrofuran Leading to Bridging Cyclic Fischer-Type Carbene Complexes

Shimogawa¹,

Konishi²,

Takao

et al. 2016

Organometallics

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“…The analogous dicationic PMe 3 complex, [Cp*(PMe 3 )Ir(μ-H)] 2 2+ , has not been reported, perhaps because the larger steric demand of the PMe 3 ligands prevents dimerization of [Cp*(PMe 3 )Ir(H)] + fragments. Analogous neutral complexes of the form [Cp*(CO)M(μ-H)] 2 have been previously reported for osmium and ruthenium; however, the reactivity of these species has not been reported. Yamaguchi and co-workers reported a similar dicationic dimer of iridium that contains the N-heterocyclic carbene ligand 1,3,4,5-tetramethylimidazol-2-ylidene in place of the CO ligands in 9 …”

Section: Resultsmentioning

confidence: 76%

Dinuclear Iridium Complexes Containing Cp* and Carbonyl Ligands: Synthesis, Structure, and Reactivity

et al. 2009

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The syntheses of the monomeric cationic complexes [Cp*(CO)Ir(R)(CH 2 Cl 2 )] were attempted (Cp* ) η 5 -C 5 Me 5 , R ) Me, H). The target complexes were not obtained; instead, dimeric products were isolated in high yields. The reaction between Cp*(CO) Ir(Me)Cl and [Li(Et 2 O) 2.5 ][BAr F 4 ] afforded the cationic complex [{Cp*(CO)Ir(Me)} 2 (µ-Cl)][BAr F 4 ] (4) in high yield. Complex 4 has been characterized by 1 H NMR, 13 C{ 1 H} NMR, and IR spectroscopies. Reaction of Cp*(CO)Ir(H) 2 with [CPh 3 ][BAr F 4 ] produced the dicationic complex [Cp*(CO)Ir(µ-H)] 2 [BAr F 4 ] 2 ( 9) in excellent yield. Complex 9 has been characterized by 1 H NMR and IR spectroscopies as well as elemental analysis and single-crystal X-ray diffraction. An X-ray structural determination was also carried out on the related complex [Cp*(Cl)Ir(µ-H)] 2 ( 14). The solid-state structures of 9 and 14 are compared briefly.

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“…A small amount of {Cp*Ru(μ-H)} 2 (μ-CO) ( 15 ) (6%) formed during the hydrogenation of 14 is confirmed by 1 H NMR signals (δ 1.79 (Cp*) and −12.88 ppm (RuH)) in C 6 D 6 . Complex 15 is produced by thermolysis of 13 at 110 °C under an Ar atmosphere.…”

Section: Results and Discussionmentioning

confidence: 79%

Catalytic Hydrogenation of Benzonitrile by Triruthenium Clusters: Consecutive Transformations of Benzonitrile on the Face of a Ru₃ Plane

et al. 2018

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Reactions of the triruthenium clusters {Cp*Ru(μ-H)}3(μ3-H)2 (1) and (Cp*Ru)3(μ3-H)(μ-H)2(μ-CO) (12) (Cp* = η5-C5Me5) with benzonitrile were investigated in relation to the selective hydrogenation of benzonitrile to benzylamine. Benzonitrile undergoes consecutive transformations into μ3-η2:η2(⊥)-nitrile, μ3-η2:η2(⊥)-imidoyl, μ3-η2(∥)-imidoyl, μ3-η2-alkylideneamido, μ3-imido, and μ-amido ligands on the Ru3 plane accompanied by the uptake of dihydrogen. The reactions are analogues of nitrile hydrogenation on a metal surface. The complexes are structural models of chemisorbed species and catalyze the hydrogenation of benzonitrile. Complex 1 catalyzes benzonitrile hydrogenation without additives but exhibits only moderate selectivity toward benzylamine. Although the μ3-benzylimido complex {Cp*Ru(μ-H)}3(μ3-NCH2Ph) (4) was obtained by reaction of 1 with benzonitrile, it was readily transformed into to the μ3-imidoyl complexes (Cp*Ru)3(μ-H)2{μ3-η2:η2(⊥)-PhCNH} (3) and (Cp*Ru)3(H)4{μ3-η2(∥∥)-PhCNH} (4), which are key intermediates in secondary imine formation. Two benzonitrile molecules were incorporated on the Ru3 plane under the reaction conditions, which decreases the selectivity of primary amine formation. In contrast, μ-carbonyl complex 12 suppresses the incorporation of additional benzonitrile ligands and the formation of μ3-imidoyl species due to the presence of CO. These features of 12 bring about significant improvement in the selectivity of benzonitrile hydrogenation and produce benzylamine in 92% yield.

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Reactions of [CpRuOMe]2. 7. Intramolecular transformation of a RuOCH3 unit into a Ru(CO)H unit: crystal and molecular structure of CpRu(.mu.-H)2(.mu.-CO)RuCp*

Cited by 26 publications

References 1 publication

Photoinduced Reactions of Diruthenium Tetrahydride Complexes: Carbon–Hydrogen Bond Cleavage of Tetrahydrofuran Leading to Bridging Cyclic Fischer-Type Carbene Complexes

Photoinduced Reactions of Diruthenium Tetrahydride Complexes: Carbon–Hydrogen Bond Cleavage of Tetrahydrofuran Leading to Bridging Cyclic Fischer-Type Carbene Complexes

Dinuclear Iridium Complexes Containing Cp* and Carbonyl Ligands: Synthesis, Structure, and Reactivity

Catalytic Hydrogenation of Benzonitrile by Triruthenium Clusters: Consecutive Transformations of Benzonitrile on the Face of a Ru₃ Plane

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Reactions of [Cp*RuOMe]2. 7. Intramolecular transformation of a RuOCH3 unit into a Ru(CO)H unit: crystal and molecular structure of Cp*Ru(.mu.-H)2(.mu.-CO)RuCp*

Cited by 26 publications

References 1 publication

Photoinduced Reactions of Diruthenium Tetrahydride Complexes: Carbon–Hydrogen Bond Cleavage of Tetrahydrofuran Leading to Bridging Cyclic Fischer-Type Carbene Complexes

Photoinduced Reactions of Diruthenium Tetrahydride Complexes: Carbon–Hydrogen Bond Cleavage of Tetrahydrofuran Leading to Bridging Cyclic Fischer-Type Carbene Complexes

Dinuclear Iridium Complexes Containing Cp* and Carbonyl Ligands: Synthesis, Structure, and Reactivity

Catalytic Hydrogenation of Benzonitrile by Triruthenium Clusters: Consecutive Transformations of Benzonitrile on the Face of a Ru3 Plane

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Reactions of [CpRuOMe]2. 7. Intramolecular transformation of a RuOCH3 unit into a Ru(CO)H unit: crystal and molecular structure of CpRu(.mu.-H)2(.mu.-CO)RuCp*

Catalytic Hydrogenation of Benzonitrile by Triruthenium Clusters: Consecutive Transformations of Benzonitrile on the Face of a Ru₃ Plane