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Theoretical Study of Reductive Functionalization of Methyl Ligands of Group 9 Complexes Supported by Two Bipyridyl Ligands: A Key Step in Catalytic Hydrocarbon Functionalization

Journal Article · · Organometallics
DOI:https://doi.org/10.1021/om4010093· OSTI ID:1607838
 [1];  [2];  [3];  [4]
  1. Univ. of North Texas, Denton, TX (United States); University of Virginia
  2. Princeton Univ., NJ (United States)
  3. Univ. of Virginia, Charlottesville, VA (United States)
  4. Univ. of North Texas, Denton, TX (United States)
+ Show Author Affiliations
A density functional theory (DFT) study was performed to consider the factors that control the reactivity of bipyridine (bpy) ligated Rh(III) methyl complexes towards nucleophiles to produce functionalized methane and Rh(I) complexes. The effect of the structure of the complex, the nucleophile, the identity of the ancillary ligand, the electronic properties of the bipyridine ligand and the identity of the metal were considered. Many similarities were found between the reaction of Rh(III) methyl complexes supported by bipyridyl ligands and classic organic SN2 reactions, including a strong dependence of the reaction on the nucleophile identity and modifications to the complex that facilitate rhodium as a leaving group. Using these concepts, a comparison of reductive functionalization of Rh(III) alkyl complexes supported by porphyrin versus two bipyridyl ligands was made, and modifications that could lead to more active complexes were proposed.
Research Organization:
Univ. of Virginia, Charlottesville, VA (United States)
Sponsoring Organization:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
Grant/Contract Number:
SC0001298
OSTI ID:
1607838
Alternate ID(s):
OSTI ID: 1161473
OSTI ID: 1383785
Journal Information:
Organometallics, Journal Name: Organometallics Journal Issue: 8 Vol. 33; ISSN 0276-7333
Publisher:
American Chemical SocietyCopyright Statement
Country of Publication:
United States
Language:
English

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Cited By (2)

Single-Electron Redox Chemistry on the [Cp*Rh] Platform Enabled by a Nitrated Bipyridyl Ligand journal November 2018
Activation of Aromatic C−C Bonds of 2,2’-Bipyridine Ligands journal October 2016

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37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY