Synthesis and dynamic properties of a triruthenium complex containing μ32(∥)-ethyne and μ3- methylidyne ligands: Equilibrium of an ethyne-hydrido complex with a nonclassical μ3-Vinyl complex

Atsushi Tahara, Mana Kajigaya, Toshiro Takao, Hiroharu Suzuki

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Abstract

A triruthenium complex containing μ32(∥) -ethyne and μ3-methylidyne ligands, (CpRu) 332(∥)-HCî-≡CH} (μ3-CH)(μ-H)2 (2a), was synthesized via the treatment of {Cp*Ru(μ-H)}33-H)2 (3) (Cp* = η5-C5Me5) with propene. In the low-temperature region, VT 1H NMR spectra showed that complex 2a is in equilibrium with a nonclassical μ3-vinyl complex, (CpRu)3322-HC= CH2)(μ3-CH)(μ-H) (5a), which features an interaction between one of the β-vinyl protons and a Ru center. The presence of the unusual 3c-2e interaction of the β-C-H bond of the vinyl group is strongly supported by the small JC-H value (98 Hz) found for the β-carbon as well as the small JH-H value for the α-vinyl proton. Treatment of the equilibrated mixture of phenyl-substituted complexes (CpRu)332(∥)-HCî- ≡CPh}(μ3-CH)(μ-H)2 (2b) and (CpRu) 3322-HC=CHPh) (μ3-CH)(μ-H) (5b) with tBuNC afforded a μ-styryl complex, (CpRu)3(μ-η2-HC=CHPh)(μ3-CH) (μ-tBuNC)(μ-H) (6), while analogous treatment of 2a and 5a resulted in the formation of μ3-dimetalloallyl complex (CpRu)333-CHCHCN(H)tBu}(μ3-CH)(μ-H) (7). These results imply that the coordinatively saturated μ3- η2(∥)-alkyne-μ3-alkylidyne complex can generate a vacant site via the migration of a hydrido ligand onto an alkyne ligand to yield a μ-vinyl intermediate.

Original languageEnglish
Pages (from-to)260-271
Number of pages12
JournalOrganometallics
Volume32
Issue number1
DOIs
Publication statusPublished - Jan 14 2013

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Acetylene
dynamic characteristics
Alkynes
methylidyne
Ligands
ligands
Protons
synthesis
alkynes
Carbon
Nuclear magnetic resonance
protons
Temperature
interactions
nuclear magnetic resonance
carbon

All Science Journal Classification (ASJC) codes

  • Physical and Theoretical Chemistry
  • Organic Chemistry
  • Inorganic Chemistry

Cite this

@article{fb43f7e9234246f381b29d27f67d9eea,
title = "Synthesis and dynamic properties of a triruthenium complex containing μ3-η2(∥)-ethyne and μ3- methylidyne ligands: Equilibrium of an ethyne-hydrido complex with a nonclassical μ3-Vinyl complex",
abstract = "A triruthenium complex containing μ3-η2(∥) -ethyne and μ3-methylidyne ligands, (CpRu) 3{μ3-η2(∥)-HC{\^i}-≡CH} (μ3-CH)(μ-H)2 (2a), was synthesized via the treatment of {Cp*Ru(μ-H)}3(μ3-H)2 (3) (Cp* = η5-C5Me5) with propene. In the low-temperature region, VT 1H NMR spectra showed that complex 2a is in equilibrium with a nonclassical μ3-vinyl complex, (CpRu)3(μ3-η2:η2-HC= CH2)(μ3-CH)(μ-H) (5a), which features an interaction between one of the β-vinyl protons and a Ru center. The presence of the unusual 3c-2e interaction of the β-C-H bond of the vinyl group is strongly supported by the small JC-H value (98 Hz) found for the β-carbon as well as the small JH-H value for the α-vinyl proton. Treatment of the equilibrated mixture of phenyl-substituted complexes (CpRu)3{μ3-η2(∥)-HC{\^i}- ≡CPh}(μ3-CH)(μ-H)2 (2b) and (CpRu) 3(μ3-η2:η2-HC=CHPh) (μ3-CH)(μ-H) (5b) with tBuNC afforded a μ-styryl complex, (CpRu)3(μ-η2-HC=CHPh)(μ3-CH) (μ-tBuNC)(μ-H) (6), while analogous treatment of 2a and 5a resulted in the formation of μ3-dimetalloallyl complex (CpRu)3{μ 3-η3-CHCHCN(H)tBu}(μ3-CH)(μ-H) (7). These results imply that the coordinatively saturated μ3- η2(∥)-alkyne-μ3-alkylidyne complex can generate a vacant site via the migration of a hydrido ligand onto an alkyne ligand to yield a μ-vinyl intermediate.",
author = "Atsushi Tahara and Mana Kajigaya and Toshiro Takao and Hiroharu Suzuki",
year = "2013",
month = "1",
day = "14",
doi = "10.1021/om301064y",
language = "English",
volume = "32",
pages = "260--271",
journal = "Organometallics",
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TY - JOUR

T1 - Synthesis and dynamic properties of a triruthenium complex containing μ3-η2(∥)-ethyne and μ3- methylidyne ligands

T2 - Equilibrium of an ethyne-hydrido complex with a nonclassical μ3-Vinyl complex

AU - Tahara, Atsushi

AU - Kajigaya, Mana

AU - Takao, Toshiro

AU - Suzuki, Hiroharu

PY - 2013/1/14

Y1 - 2013/1/14

N2 - A triruthenium complex containing μ3-η2(∥) -ethyne and μ3-methylidyne ligands, (CpRu) 3{μ3-η2(∥)-HCî-≡CH} (μ3-CH)(μ-H)2 (2a), was synthesized via the treatment of {Cp*Ru(μ-H)}3(μ3-H)2 (3) (Cp* = η5-C5Me5) with propene. In the low-temperature region, VT 1H NMR spectra showed that complex 2a is in equilibrium with a nonclassical μ3-vinyl complex, (CpRu)3(μ3-η2:η2-HC= CH2)(μ3-CH)(μ-H) (5a), which features an interaction between one of the β-vinyl protons and a Ru center. The presence of the unusual 3c-2e interaction of the β-C-H bond of the vinyl group is strongly supported by the small JC-H value (98 Hz) found for the β-carbon as well as the small JH-H value for the α-vinyl proton. Treatment of the equilibrated mixture of phenyl-substituted complexes (CpRu)3{μ3-η2(∥)-HCî- ≡CPh}(μ3-CH)(μ-H)2 (2b) and (CpRu) 3(μ3-η2:η2-HC=CHPh) (μ3-CH)(μ-H) (5b) with tBuNC afforded a μ-styryl complex, (CpRu)3(μ-η2-HC=CHPh)(μ3-CH) (μ-tBuNC)(μ-H) (6), while analogous treatment of 2a and 5a resulted in the formation of μ3-dimetalloallyl complex (CpRu)3{μ 3-η3-CHCHCN(H)tBu}(μ3-CH)(μ-H) (7). These results imply that the coordinatively saturated μ3- η2(∥)-alkyne-μ3-alkylidyne complex can generate a vacant site via the migration of a hydrido ligand onto an alkyne ligand to yield a μ-vinyl intermediate.

AB - A triruthenium complex containing μ3-η2(∥) -ethyne and μ3-methylidyne ligands, (CpRu) 3{μ3-η2(∥)-HCî-≡CH} (μ3-CH)(μ-H)2 (2a), was synthesized via the treatment of {Cp*Ru(μ-H)}3(μ3-H)2 (3) (Cp* = η5-C5Me5) with propene. In the low-temperature region, VT 1H NMR spectra showed that complex 2a is in equilibrium with a nonclassical μ3-vinyl complex, (CpRu)3(μ3-η2:η2-HC= CH2)(μ3-CH)(μ-H) (5a), which features an interaction between one of the β-vinyl protons and a Ru center. The presence of the unusual 3c-2e interaction of the β-C-H bond of the vinyl group is strongly supported by the small JC-H value (98 Hz) found for the β-carbon as well as the small JH-H value for the α-vinyl proton. Treatment of the equilibrated mixture of phenyl-substituted complexes (CpRu)3{μ3-η2(∥)-HCî- ≡CPh}(μ3-CH)(μ-H)2 (2b) and (CpRu) 3(μ3-η2:η2-HC=CHPh) (μ3-CH)(μ-H) (5b) with tBuNC afforded a μ-styryl complex, (CpRu)3(μ-η2-HC=CHPh)(μ3-CH) (μ-tBuNC)(μ-H) (6), while analogous treatment of 2a and 5a resulted in the formation of μ3-dimetalloallyl complex (CpRu)3{μ 3-η3-CHCHCN(H)tBu}(μ3-CH)(μ-H) (7). These results imply that the coordinatively saturated μ3- η2(∥)-alkyne-μ3-alkylidyne complex can generate a vacant site via the migration of a hydrido ligand onto an alkyne ligand to yield a μ-vinyl intermediate.

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