Ammonia Synthesis by Hydrogenolysis of Titanium-Nitrogen Bonds Using Proton Coupled Electron Transfer

Iraklis Pappas; Paul J. Chirik

doi:10.1021/jacs.5b01047

Ammonia Synthesis by Hydrogenolysis of Titanium-Nitrogen Bonds Using Proton Coupled Electron Transfer

Iraklis Pappas, Paul J. Chirik

Chemistry

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65 Scopus citations

Abstract

The catalytic hydrogenolysis of the titanium-amide bond in (η⁵-C₅Me₄SiMe₃)₂Ti(Cl)NH₂ to yield free ammonia is described. The rhodium hydride, (η⁵-C₅Me₅)(py-Ph)RhH (py-Ph = 2-phenylpyridine), serves as the catalyst and promotes N-H bond formation via hydrogen atom transfer. The N-H bond dissociation free energies of ammonia ligands have also been determined for titanocene and zirconocene complexes and reveal a stark dependence on metal identity and oxidation state. In all cases, the N-H BDFEs of coordinated NH₃ decreases by >40 kcal/mol from the value in the free gas phase molecule.

Original language	English (US)
Pages (from-to)	3498-3501
Number of pages	4
Journal	Journal of the American Chemical Society
Volume	137
Issue number	10
DOIs	https://doi.org/10.1021/jacs.5b01047
State	Published - Mar 18 2015

All Science Journal Classification (ASJC) codes

Catalysis
General Chemistry
Biochemistry
Colloid and Surface Chemistry

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10.1021/jacs.5b01047

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title = "Ammonia Synthesis by Hydrogenolysis of Titanium-Nitrogen Bonds Using Proton Coupled Electron Transfer",

abstract = "The catalytic hydrogenolysis of the titanium-amide bond in (η5-C5Me4SiMe3)2Ti(Cl)NH2 to yield free ammonia is described. The rhodium hydride, (η5-C5Me5)(py-Ph)RhH (py-Ph = 2-phenylpyridine), serves as the catalyst and promotes N-H bond formation via hydrogen atom transfer. The N-H bond dissociation free energies of ammonia ligands have also been determined for titanocene and zirconocene complexes and reveal a stark dependence on metal identity and oxidation state. In all cases, the N-H BDFEs of coordinated NH3 decreases by >40 kcal/mol from the value in the free gas phase molecule.",

author = "Iraklis Pappas and Chirik, {Paul J.}",

note = "Publisher Copyright: {\textcopyright} 2015 American Chemical Society.",

year = "2015",

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AU - Pappas, Iraklis

AU - Chirik, Paul J.

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N2 - The catalytic hydrogenolysis of the titanium-amide bond in (η5-C5Me4SiMe3)2Ti(Cl)NH2 to yield free ammonia is described. The rhodium hydride, (η5-C5Me5)(py-Ph)RhH (py-Ph = 2-phenylpyridine), serves as the catalyst and promotes N-H bond formation via hydrogen atom transfer. The N-H bond dissociation free energies of ammonia ligands have also been determined for titanocene and zirconocene complexes and reveal a stark dependence on metal identity and oxidation state. In all cases, the N-H BDFEs of coordinated NH3 decreases by >40 kcal/mol from the value in the free gas phase molecule.

AB - The catalytic hydrogenolysis of the titanium-amide bond in (η5-C5Me4SiMe3)2Ti(Cl)NH2 to yield free ammonia is described. The rhodium hydride, (η5-C5Me5)(py-Ph)RhH (py-Ph = 2-phenylpyridine), serves as the catalyst and promotes N-H bond formation via hydrogen atom transfer. The N-H bond dissociation free energies of ammonia ligands have also been determined for titanocene and zirconocene complexes and reveal a stark dependence on metal identity and oxidation state. In all cases, the N-H BDFEs of coordinated NH3 decreases by >40 kcal/mol from the value in the free gas phase molecule.

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Ammonia Synthesis by Hydrogenolysis of Titanium-Nitrogen Bonds Using Proton Coupled Electron Transfer

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