Aryl C-H amination by diruthenium nitrides in the solid state and in solution at room temperature: Experimental and computational study of the reaction mechanism

Amanda Kae Musch Long, George H. Timmer, J. Pap, Jamie Lynn Snyder, Renyuan Pony Yu, John F. Berry

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Abstract

Diruthenium azido complexes Ru2(DPhF)4N3 (1a, DPhF = N,N'-diphenylformamidinate) and Ru2(D(3,5-Cl 2)PhF)4N3 (1b, D(3,5-Cl2)PhF = N,N'-bis(3,5-dichlorophenyl)formamidinate) have been investigated by thermolytic and photolytic experiments to investigate the chemical reactivity of the corresponding diruthenium nitride species. Thermolysis of 1b at ∼100 °C leads to the expulsion of N2 and isolation of Ru2(D(3,5- Cl2)PhF)3NH(C13H6N 2Cl4) (3b), in which a nitrogen atom has been inserted into one of the proximal aryl C-H bonds of a D(3,5-Cl2)PhF ligand. A similar C-H insertion product is obtained upon thawing a frozen CH 2Cl2 solution of the nitride complex Ru 2(DPhF)4N (2a), formed via photolysis at -196 °C of 1a to yield Ru2(DPhF)3NH(C13H10N 2) (3a). Evidence is provided here that both reactions proceed via direct intramolecular attack of an electrophilic terminal nitrido nitrogen atom on a proximal aryl ring. Thermodynamic and kinetic data for this reaction are obtained from differential scanning calorimetric measurements and thermal gravimetric analysis of the thermolysis of Ru2(D(3,5-Cl 2)PhF)4N3, and by Arrhenius/Eyring analysis of the conversion of Ru2(DPhF)4N to its C-H insertion product, respectively. These data are used to develop a detailed, experimentally validated DFT reaction pathway for N2 extrusion and C-H functionalization from Ru2(D(3,5-Cl2)PhF) 4N3. The diruthenium nitrido complex is an intermediate in the calculated reaction pathway, and the C-H functionalization event shares a close resemblance to a classical electrophilic aromatic substitution mechanism.

Original languageEnglish
Pages (from-to)13138-13150
Number of pages13
JournalJournal of the American Chemical Society
Volume133
Issue number33
DOIs
Publication statusPublished - Aug 24 2011

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Amination
Thermolysis
Nitrides
Nitrogen
Atoms
Chemical reactivity
Temperature
Thawing
Gravimetric analysis
Photolysis
Thermodynamics
Discrete Fourier transforms
Extrusion
Substitution reactions
Hot Temperature
Ligands
Scanning
Kinetics
Experiments

ASJC Scopus subject areas

  • Chemistry(all)
  • Catalysis
  • Biochemistry
  • Colloid and Surface Chemistry

Cite this

Aryl C-H amination by diruthenium nitrides in the solid state and in solution at room temperature : Experimental and computational study of the reaction mechanism. / Long, Amanda Kae Musch; Timmer, George H.; Pap, J.; Snyder, Jamie Lynn; Yu, Renyuan Pony; Berry, John F.

In: Journal of the American Chemical Society, Vol. 133, No. 33, 24.08.2011, p. 13138-13150.

Research output: Contribution to journalArticle

Long, Amanda Kae Musch ; Timmer, George H. ; Pap, J. ; Snyder, Jamie Lynn ; Yu, Renyuan Pony ; Berry, John F. / Aryl C-H amination by diruthenium nitrides in the solid state and in solution at room temperature : Experimental and computational study of the reaction mechanism. In: Journal of the American Chemical Society. 2011 ; Vol. 133, No. 33. pp. 13138-13150.
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abstract = "Diruthenium azido complexes Ru2(DPhF)4N3 (1a, DPhF = N,N'-diphenylformamidinate) and Ru2(D(3,5-Cl 2)PhF)4N3 (1b, D(3,5-Cl2)PhF = N,N'-bis(3,5-dichlorophenyl)formamidinate) have been investigated by thermolytic and photolytic experiments to investigate the chemical reactivity of the corresponding diruthenium nitride species. Thermolysis of 1b at ∼100 °C leads to the expulsion of N2 and isolation of Ru2(D(3,5- Cl2)PhF)3NH(C13H6N 2Cl4) (3b), in which a nitrogen atom has been inserted into one of the proximal aryl C-H bonds of a D(3,5-Cl2)PhF ligand. A similar C-H insertion product is obtained upon thawing a frozen CH 2Cl2 solution of the nitride complex Ru 2(DPhF)4N (2a), formed via photolysis at -196 °C of 1a to yield Ru2(DPhF)3NH(C13H10N 2) (3a). Evidence is provided here that both reactions proceed via direct intramolecular attack of an electrophilic terminal nitrido nitrogen atom on a proximal aryl ring. Thermodynamic and kinetic data for this reaction are obtained from differential scanning calorimetric measurements and thermal gravimetric analysis of the thermolysis of Ru2(D(3,5-Cl 2)PhF)4N3, and by Arrhenius/Eyring analysis of the conversion of Ru2(DPhF)4N to its C-H insertion product, respectively. These data are used to develop a detailed, experimentally validated DFT reaction pathway for N2 extrusion and C-H functionalization from Ru2(D(3,5-Cl2)PhF) 4N3. The diruthenium nitrido complex is an intermediate in the calculated reaction pathway, and the C-H functionalization event shares a close resemblance to a classical electrophilic aromatic substitution mechanism.",
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N2 - Diruthenium azido complexes Ru2(DPhF)4N3 (1a, DPhF = N,N'-diphenylformamidinate) and Ru2(D(3,5-Cl 2)PhF)4N3 (1b, D(3,5-Cl2)PhF = N,N'-bis(3,5-dichlorophenyl)formamidinate) have been investigated by thermolytic and photolytic experiments to investigate the chemical reactivity of the corresponding diruthenium nitride species. Thermolysis of 1b at ∼100 °C leads to the expulsion of N2 and isolation of Ru2(D(3,5- Cl2)PhF)3NH(C13H6N 2Cl4) (3b), in which a nitrogen atom has been inserted into one of the proximal aryl C-H bonds of a D(3,5-Cl2)PhF ligand. A similar C-H insertion product is obtained upon thawing a frozen CH 2Cl2 solution of the nitride complex Ru 2(DPhF)4N (2a), formed via photolysis at -196 °C of 1a to yield Ru2(DPhF)3NH(C13H10N 2) (3a). Evidence is provided here that both reactions proceed via direct intramolecular attack of an electrophilic terminal nitrido nitrogen atom on a proximal aryl ring. Thermodynamic and kinetic data for this reaction are obtained from differential scanning calorimetric measurements and thermal gravimetric analysis of the thermolysis of Ru2(D(3,5-Cl 2)PhF)4N3, and by Arrhenius/Eyring analysis of the conversion of Ru2(DPhF)4N to its C-H insertion product, respectively. These data are used to develop a detailed, experimentally validated DFT reaction pathway for N2 extrusion and C-H functionalization from Ru2(D(3,5-Cl2)PhF) 4N3. The diruthenium nitrido complex is an intermediate in the calculated reaction pathway, and the C-H functionalization event shares a close resemblance to a classical electrophilic aromatic substitution mechanism.

AB - Diruthenium azido complexes Ru2(DPhF)4N3 (1a, DPhF = N,N'-diphenylformamidinate) and Ru2(D(3,5-Cl 2)PhF)4N3 (1b, D(3,5-Cl2)PhF = N,N'-bis(3,5-dichlorophenyl)formamidinate) have been investigated by thermolytic and photolytic experiments to investigate the chemical reactivity of the corresponding diruthenium nitride species. Thermolysis of 1b at ∼100 °C leads to the expulsion of N2 and isolation of Ru2(D(3,5- Cl2)PhF)3NH(C13H6N 2Cl4) (3b), in which a nitrogen atom has been inserted into one of the proximal aryl C-H bonds of a D(3,5-Cl2)PhF ligand. A similar C-H insertion product is obtained upon thawing a frozen CH 2Cl2 solution of the nitride complex Ru 2(DPhF)4N (2a), formed via photolysis at -196 °C of 1a to yield Ru2(DPhF)3NH(C13H10N 2) (3a). Evidence is provided here that both reactions proceed via direct intramolecular attack of an electrophilic terminal nitrido nitrogen atom on a proximal aryl ring. Thermodynamic and kinetic data for this reaction are obtained from differential scanning calorimetric measurements and thermal gravimetric analysis of the thermolysis of Ru2(D(3,5-Cl 2)PhF)4N3, and by Arrhenius/Eyring analysis of the conversion of Ru2(DPhF)4N to its C-H insertion product, respectively. These data are used to develop a detailed, experimentally validated DFT reaction pathway for N2 extrusion and C-H functionalization from Ru2(D(3,5-Cl2)PhF) 4N3. The diruthenium nitrido complex is an intermediate in the calculated reaction pathway, and the C-H functionalization event shares a close resemblance to a classical electrophilic aromatic substitution mechanism.

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