Reaction of nitromethane with an iridium pincer complex. Multiple binding modes of the nitromethanate anion

Xiawei Zhang, Thomas J. Emge, Rajshekhar Ghosh, Karsten Krogh-Jespersen, Alan S Goldman

Research output: Contribution to journalArticle

18 Citations (Scopus)

Abstract

The reaction of nitromethane with (PCP)Ir (PCP = κ 3-2,6- ( tBu 2PCH 2) 2C 6H 3) yields the bidentate O,O-ligated nitromethanate complex (PCP)Ir(H)(κ 2-O,O-NO 2CH 2) (1). Reaction of 1 with CO affords a CO adduct with a mono-oxygen-ligated nitromethanate, 2, which represents the first characterized transition metal mono-oxygen-ligated nitromethanate complex. At elevated temperature, complex 2 isomerizes to give the carbon-bound nitromethyl complex 3. Complex 1 also undergoes addition of cyclohexylisocyanide (analogous to the reaction with CO) to form the mono-oxygen-ligated nitromethanate complex 4, which also isomerizes to form the corresponding nitromethyl complex, 5. The (PCP)Ir-(CH 3NO 2) system is the first species known to display three binding modes with a nitromethanate anion. Results from density functional calculations illustrate the structures and energies of the minima and transition states on the potential energy surfaces. The calculations suggest that 1 is the thermodynamic product of (PCP)Ir reacting with nitromethane; a kinetic product, formed via oxidative addition of a nitromethane C-H bond, should readily rearrange to form 1.

Original languageEnglish
Pages (from-to)1303-1309
Number of pages7
JournalOrganometallics
Volume25
Issue number5
DOIs
Publication statusPublished - Feb 27 2006

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Iridium
nitromethane
Carbon Monoxide
iridium
Anions
Oxygen
anions
oxygen
Potential energy surfaces
products
adducts
Transition metals
Density functional theory
Carbon
transition metals
potential energy
Thermodynamics
methylidyne
thermodynamics
Kinetics

ASJC Scopus subject areas

  • Inorganic Chemistry
  • Organic Chemistry

Cite this

Reaction of nitromethane with an iridium pincer complex. Multiple binding modes of the nitromethanate anion. / Zhang, Xiawei; Emge, Thomas J.; Ghosh, Rajshekhar; Krogh-Jespersen, Karsten; Goldman, Alan S.

In: Organometallics, Vol. 25, No. 5, 27.02.2006, p. 1303-1309.

Research output: Contribution to journalArticle

Zhang, Xiawei ; Emge, Thomas J. ; Ghosh, Rajshekhar ; Krogh-Jespersen, Karsten ; Goldman, Alan S. / Reaction of nitromethane with an iridium pincer complex. Multiple binding modes of the nitromethanate anion. In: Organometallics. 2006 ; Vol. 25, No. 5. pp. 1303-1309.
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abstract = "The reaction of nitromethane with (PCP)Ir (PCP = κ 3-2,6- ( tBu 2PCH 2) 2C 6H 3) yields the bidentate O,O-ligated nitromethanate complex (PCP)Ir(H)(κ 2-O,O-NO 2CH 2) (1). Reaction of 1 with CO affords a CO adduct with a mono-oxygen-ligated nitromethanate, 2, which represents the first characterized transition metal mono-oxygen-ligated nitromethanate complex. At elevated temperature, complex 2 isomerizes to give the carbon-bound nitromethyl complex 3. Complex 1 also undergoes addition of cyclohexylisocyanide (analogous to the reaction with CO) to form the mono-oxygen-ligated nitromethanate complex 4, which also isomerizes to form the corresponding nitromethyl complex, 5. The (PCP)Ir-(CH 3NO 2) system is the first species known to display three binding modes with a nitromethanate anion. Results from density functional calculations illustrate the structures and energies of the minima and transition states on the potential energy surfaces. The calculations suggest that 1 is the thermodynamic product of (PCP)Ir reacting with nitromethane; a kinetic product, formed via oxidative addition of a nitromethane C-H bond, should readily rearrange to form 1.",
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