1,3-Dipolar Cycloaddition Reactions of Low-Valent Rhodium and Iridium Complexes with Arylnitrile N-Oxides

  1. Ugur, I. 23
  2. Agopcan Cinar, S. 2
  3. Dedeoglu, B. 4
  4. Aviyente, V. 2
  5. Hawthorne, M.F. 5
  6. Liu, P. 3
  7. Liu, F. 3
  8. Houk, K.N. 3
  9. Jiménez-Osés, G. 1
  1. 1 Universidad de La Rioja
    info

    Universidad de La Rioja

    Logroño, España

    ROR https://ror.org/0553yr311

  2. 2 Boğaziçi University
    info

    Boğaziçi University

    Estambul, Turquía

    ROR https://ror.org/03z9tma90

  3. 3 University of California Los Angeles
    info

    University of California Los Angeles

    Los Ángeles, Estados Unidos

    ROR https://ror.org/046rm7j60

  4. 4 Sabancı University
    info

    Sabancı University

    Estambul, Turquía

    ROR https://ror.org/049asqa32

  5. 5 University of Missouri
    info

    University of Missouri

    Columbia, Estados Unidos

    ROR https://ror.org/02ymw8z06

Erakutsi afiliazioak +
Aldizkaria:
Journal of Organic Chemistry

ISSN: 0022-3263

Argitalpen urtea: 2017

Alea: 82

Zenbakia: 10

Orrialdeak: 5096-5101

Mota: Artikulua

DOI: 10.1021/ACS.JOC.7B00282 SCOPUS: 2-s2.0-85019348691 WoS: WOS:000402023200008 GOOGLE SCHOLAR

Beste argitalpen batzuk: Journal of Organic Chemistry

Lotura duten proiektuak

Una metodología computacional multi-escala para la modificación selectiva de proteínas y la reprogamación de enzimas.

2016/00015/001

Laburpena

The reactions between low-valent Rh(I) and Ir(I) metal-carbonyl complexes and arylnitrile oxides possess the electronic and structural features of 1,3-dipolar cycloadditions. Density functional theory (DFT) calculations on these reactions, involving both cyclopentadienyl and carboranyl ligands on the metal carbonyl, explain the ease of the chemical processes and the stabilities of the resulting metallaisoxazolin-5-ones. The metal-carbonyl bond has partial double bond character according to the Wiberg index calculated through NBO analysis, and so the reaction can be considered a normal 1,3-dipolar cycloaddition involving M=C bonds. The rates of formation of the metallacycloadducts are controlled by distortion energy, analogous to their organic counterparts. The superior ability of anionic Ir complexes to share their electron density and accommodate higher oxidation states explains their calculated higher reactivity toward cycloaddition, as compared to Rh analogues. © 2017 American Chemical Society.