The reaction of ortho-halogenated aromatic aldazine ligands with Fe2(CO)9: symmetrical cleavage of the azine and carbon–halogen activation

The reaction of a triruthenium pentahydrido complex, {Cp*Ru(μ-H)}3(μ3-H)2 (1; Cp* = η5-C5Me5), with N-benzylidenemethylamine resulted in the exclusive formation of a perpendicularly coordinated iminoacyl complex, (Cp*Ru)3(μ-η2:η2(⊥)-PhCNMe)(μ-H)2 (3b), as a result of C–H bond scission of imine. However, the treatment of 1 with N-benzylideneaniline at 100 °C caused C–N bond cleavage to yield the μ3-benzylidyne−μ3-phenylimido complex (Cp*Ru)3(μ3-CPh)(μ3-NPh)(μ-H)2 (7c) and the μ3-methylidyne−μ3-phenylimido complex (Cp*Ru)3(μ3-CH)(μ3-NPh)(μ-H)2 (8). The formation of 7c is in strong contrast to the C–N bond scission occurred in (Cp*Ru)3(μ-η2:η2(⊥)-PhCNH)(μ-H)2 (3a), which required heating at 180 °C. The structural and spectral properties of μ3-η2:η2(⊥)-nitrile complex 2, cationic μ3-η2:η2(⊥)-iminoacyl complex 6, and neutral μ3-η2:η2(⊥)-iminoacyl complex 3 revealed a clear trend of the activation of the C–N bond on a Ru3 plane. The thermolysis of 3b proceeded in a different manner to yield a μ3-methylidyne−μ3-η2(∥)-iminoacyl complex, (Cp*Ru)3(μ3-CH)(μ3-HNCH)(μ-H) (9), as a consequence of both C–N and C–C bond scission.

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“…Data for (Cp*Ru) 3 (μ-H) 2 {μ 3 -CC 6 H 4 (OMe)}(μ 3 -NPh) (7d) are as follows. C,57.37;H,6.46;N,1.52. Found: C,57.57;H,6.50;N,1.63.…”

Section: ■ Experimental Sectionmentioning

confidence: 99%

Reactions of a Triruthenium Pentahydrido Complex with Imines Leading to the Formation of a Perpendicularly Coordinated Iminoacyl Ligand and the Scission of a C═N Bond on a Triruthenium Plane

et al. 2012

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“…This iron carbon bond length Scheme 3. ranges from 228.1(2) pm (33) to 246.7(2) pm (35). In addition, the iron iron bond lengths also shows different values ranging from 241.24(4) pm (35) to 245.51(4) pm (34). Compared to the standard deviations these differences are unequivocally significant.…”

Section: Resultsmentioning

confidence: 89%

“…The most important exception from this finding is the bond length between the apical iron atom Fe ap and the carbon atom (C b in Scheme 1) next to the methylene group which was formed by the hydrogen transfer reaction. This iron carbon bond length Scheme 3. ranges from 228.1(2) pm (33) to 246.7(2) pm (35). In addition, the iron iron bond lengths also shows different values ranging from 241.24(4) pm (35) to 245.51(4) pm (34).…”

Section: Resultsmentioning

confidence: 99%

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The variation of coordination modes of aromatic imines in iron carbonyl complexes: Is there a correlation between bond lengths in organometallic model compounds and the reactivity of the ligands in catalytic C–C bond formation reactions?

Imhof

Göbel

Schweda

et al. 2005

Journal of Organometallic Chemistry

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“…Aryl chlorides are important starting materials and intermediates for organic synthesis and can be used in synthetic materials, polymers, pharmaceuticals, dyes, agrochemicals, etc. Over the years, platinum, 31 tungsten, 32 rhodium, 33 nickel, 34 rhenium, 35 copper, 36 and iron 37 complexes have been reported for the activation of C-Cl bonds. Density functional theory calculations have been employed by Macgregor to model the double C-Cl bond activation of CH 2 Cl 2 with CoCl(PR 3 ) 3 to give CoCl 3 (CH 2 PR 3 )(PR 3 ) 2 in dichloromethane solution.…”

Section: Introductionmentioning

confidence: 99%

C–Cl bond activation and catalytic hydrodechlorination of hexachlorobenzene by cobalt and nickel complexes with sodium formate as a reducing agent

Wang

et al. 2014

Dalton Trans.

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A benzyne cobalt complex, Co(η(2)-C6Cl4)(PMe3)3 (2), was generated from the reaction of hexachlorobenzene with 2 equiv. of Co(PMe3)4 through selective activation of two C-Cl bonds of hexachlorobenzene. Meanwhile, the byproduct CoCl2(PMe3)3 was also confirmed by IR spectra. The cobalt(II) complex, CoCl(C6Cl5)(PMe3)3 (1), as an intermediate in the formation of aryne complex 2, was also isolated by the reaction of hexachlorobenzene with the stoichiometric amount of Co(PMe3)4. Complex 2 could be obtained by the reaction of 1 with Co(PMe3)4. Under similar reaction conditions, the reaction of Ni(PMe3)4 with hexachlorobenzene afforded only a mono-(C-Cl) bond activation nickel(II) complex, NiCl(C6H5)(PMe3)2 (5). The expected benzyne nickel complex was not formed. The structures of complexes 2 and 5 were determined by X-ray single crystal diffraction. Successful selective hydrodechlorinations of hexachlorobenzene were studied and in the presence of Co(PMe3)4 or Ni(PMe3)4 as catalysts and sodium formate as a reducing agent pentachlorobenzene and 1,2,4,5-tetrachlorobenzene were obtained. The catalytic hydrodechlorination mechanism is proposed and discussed.

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The reaction of ortho-halogenated aromatic aldazine ligands with Fe2(CO)9: symmetrical cleavage of the azine and carbon–halogen activation

Cited by 19 publications

References 55 publications

Reactions of a Triruthenium Pentahydrido Complex with Imines Leading to the Formation of a Perpendicularly Coordinated Iminoacyl Ligand and the Scission of a C═N Bond on a Triruthenium Plane

Reactions of a Triruthenium Pentahydrido Complex with Imines Leading to the Formation of a Perpendicularly Coordinated Iminoacyl Ligand and the Scission of a C═N Bond on a Triruthenium Plane

The variation of coordination modes of aromatic imines in iron carbonyl complexes: Is there a correlation between bond lengths in organometallic model compounds and the reactivity of the ligands in catalytic C–C bond formation reactions?

C–Cl bond activation and catalytic hydrodechlorination of hexachlorobenzene by cobalt and nickel complexes with sodium formate as a reducing agent

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