Distinct Thermodynamics for the Formation and Cleavage of N-H Bonds in Aniline and Ammonia. Directly-Observed Reductive Elimination of Ammonia from an Isolated Amido Hydride Complex

Mira Kanzelberger, Xiawei Zhang, Thomas J. Emge, Alan S Goldman, Jing Zhao, Christopher Incarvito, John F. Hartwig

Research output: Contribution to journalArticle

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Abstract

The reactions of aryl and alkylamines with the (PCP)Ir fragment (PCP = 1,3-di-tert-butylphosphinobenzene) were studied to determine the reactivities and stabilities of amine and amido hydride complexes relative to C?H activation products. Reaction of aniline with the (PCP)Ir unit generated from (PCP)IrH2 and norbornene resulted in the N?H oxidative addition product (PhNH)(H)Ir(PCP) (1a). In contrast, reaction of this fragment with ammonia gave the ammonia complex (NH3)Ir(PCP) (2). The amido hydride complex that would be formed by oxidative addition of ammonia, (PCP)Ir(NH2)(H) (1b), was generated independently by deprotonation of the ammonia complex (NH3)Ir(H)(Cl)(PCP) (3) with KN(SiMe3)2 at low temperature. This amido hydride complex underwent reductive elimination at room temperature to form the ammonia complex 2. Addition of CO to anilide complex 1a gave (PCP)Ir(PhNH)(H)(CO) (4a). Addition of CNtBu to terminal amido complex 1b formed (PCP)Ir(NH2)(H)(CNtBu) (4b), the first structurally characterized iridium amido hydride. Complexes 4a and 4b underwent reductive elimination of aniline and ammonia; parent amido complex 4b reacted faster than anilide 4a. These observations suggest distinct thermodynamics for the formation and cleavage of N?H bonds in aniline and ammonia. Complexes 1a, 2, 4a, and 4b were characterized by single-crystal X-ray diffraction methods.

Original languageEnglish
Pages (from-to)13644-13645
Number of pages2
JournalJournal of the American Chemical Society
Volume125
Issue number45
DOIs
Publication statusPublished - Nov 12 2003

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Aniline
Thermodynamics
Ammonia
Hydrides
Anilides
Carbon Monoxide
Iridium
Deprotonation
Temperature
aniline
X-Ray Diffraction
Amines
Chemical activation
Single crystals
X ray diffraction
Hydrogen

ASJC Scopus subject areas

  • Chemistry(all)

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Distinct Thermodynamics for the Formation and Cleavage of N-H Bonds in Aniline and Ammonia. Directly-Observed Reductive Elimination of Ammonia from an Isolated Amido Hydride Complex. / Kanzelberger, Mira; Zhang, Xiawei; Emge, Thomas J.; Goldman, Alan S; Zhao, Jing; Incarvito, Christopher; Hartwig, John F.

In: Journal of the American Chemical Society, Vol. 125, No. 45, 12.11.2003, p. 13644-13645.

Research output: Contribution to journalArticle

Kanzelberger, Mira ; Zhang, Xiawei ; Emge, Thomas J. ; Goldman, Alan S ; Zhao, Jing ; Incarvito, Christopher ; Hartwig, John F. / Distinct Thermodynamics for the Formation and Cleavage of N-H Bonds in Aniline and Ammonia. Directly-Observed Reductive Elimination of Ammonia from an Isolated Amido Hydride Complex. In: Journal of the American Chemical Society. 2003 ; Vol. 125, No. 45. pp. 13644-13645.
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abstract = "The reactions of aryl and alkylamines with the (PCP)Ir fragment (PCP = 1,3-di-tert-butylphosphinobenzene) were studied to determine the reactivities and stabilities of amine and amido hydride complexes relative to C?H activation products. Reaction of aniline with the (PCP)Ir unit generated from (PCP)IrH2 and norbornene resulted in the N?H oxidative addition product (PhNH)(H)Ir(PCP) (1a). In contrast, reaction of this fragment with ammonia gave the ammonia complex (NH3)Ir(PCP) (2). The amido hydride complex that would be formed by oxidative addition of ammonia, (PCP)Ir(NH2)(H) (1b), was generated independently by deprotonation of the ammonia complex (NH3)Ir(H)(Cl)(PCP) (3) with KN(SiMe3)2 at low temperature. This amido hydride complex underwent reductive elimination at room temperature to form the ammonia complex 2. Addition of CO to anilide complex 1a gave (PCP)Ir(PhNH)(H)(CO) (4a). Addition of CNtBu to terminal amido complex 1b formed (PCP)Ir(NH2)(H)(CNtBu) (4b), the first structurally characterized iridium amido hydride. Complexes 4a and 4b underwent reductive elimination of aniline and ammonia; parent amido complex 4b reacted faster than anilide 4a. These observations suggest distinct thermodynamics for the formation and cleavage of N?H bonds in aniline and ammonia. Complexes 1a, 2, 4a, and 4b were characterized by single-crystal X-ray diffraction methods.",
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T1 - Distinct Thermodynamics for the Formation and Cleavage of N-H Bonds in Aniline and Ammonia. Directly-Observed Reductive Elimination of Ammonia from an Isolated Amido Hydride Complex

AU - Kanzelberger, Mira

AU - Zhang, Xiawei

AU - Emge, Thomas J.

AU - Goldman, Alan S

AU - Zhao, Jing

AU - Incarvito, Christopher

AU - Hartwig, John F.

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N2 - The reactions of aryl and alkylamines with the (PCP)Ir fragment (PCP = 1,3-di-tert-butylphosphinobenzene) were studied to determine the reactivities and stabilities of amine and amido hydride complexes relative to C?H activation products. Reaction of aniline with the (PCP)Ir unit generated from (PCP)IrH2 and norbornene resulted in the N?H oxidative addition product (PhNH)(H)Ir(PCP) (1a). In contrast, reaction of this fragment with ammonia gave the ammonia complex (NH3)Ir(PCP) (2). The amido hydride complex that would be formed by oxidative addition of ammonia, (PCP)Ir(NH2)(H) (1b), was generated independently by deprotonation of the ammonia complex (NH3)Ir(H)(Cl)(PCP) (3) with KN(SiMe3)2 at low temperature. This amido hydride complex underwent reductive elimination at room temperature to form the ammonia complex 2. Addition of CO to anilide complex 1a gave (PCP)Ir(PhNH)(H)(CO) (4a). Addition of CNtBu to terminal amido complex 1b formed (PCP)Ir(NH2)(H)(CNtBu) (4b), the first structurally characterized iridium amido hydride. Complexes 4a and 4b underwent reductive elimination of aniline and ammonia; parent amido complex 4b reacted faster than anilide 4a. These observations suggest distinct thermodynamics for the formation and cleavage of N?H bonds in aniline and ammonia. Complexes 1a, 2, 4a, and 4b were characterized by single-crystal X-ray diffraction methods.

AB - The reactions of aryl and alkylamines with the (PCP)Ir fragment (PCP = 1,3-di-tert-butylphosphinobenzene) were studied to determine the reactivities and stabilities of amine and amido hydride complexes relative to C?H activation products. Reaction of aniline with the (PCP)Ir unit generated from (PCP)IrH2 and norbornene resulted in the N?H oxidative addition product (PhNH)(H)Ir(PCP) (1a). In contrast, reaction of this fragment with ammonia gave the ammonia complex (NH3)Ir(PCP) (2). The amido hydride complex that would be formed by oxidative addition of ammonia, (PCP)Ir(NH2)(H) (1b), was generated independently by deprotonation of the ammonia complex (NH3)Ir(H)(Cl)(PCP) (3) with KN(SiMe3)2 at low temperature. This amido hydride complex underwent reductive elimination at room temperature to form the ammonia complex 2. Addition of CO to anilide complex 1a gave (PCP)Ir(PhNH)(H)(CO) (4a). Addition of CNtBu to terminal amido complex 1b formed (PCP)Ir(NH2)(H)(CNtBu) (4b), the first structurally characterized iridium amido hydride. Complexes 4a and 4b underwent reductive elimination of aniline and ammonia; parent amido complex 4b reacted faster than anilide 4a. These observations suggest distinct thermodynamics for the formation and cleavage of N?H bonds in aniline and ammonia. Complexes 1a, 2, 4a, and 4b were characterized by single-crystal X-ray diffraction methods.

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