Preparation and reactivity of macrocyclic rhodium(III) alkyl complexes

Journal Article · Sat Sep 21 00:00:00 EDT 2013 · Inorganica Chimica Acta

DOI:https://doi.org/10.1016/j.ica.2013.09.022· OSTI ID:1134202

Carraher, Jack M. ^[1]; Ellern, Arkady ^[2]; Bakac, Andreja ^[1]

---

1. Ames Lab., Ames, IA (United States); Iowa State Univ., Ames, IA (United States)
2. Iowa State Univ., Ames, IA (United States)

We found that the macrocyclic rhodium(II) complexes LRh(H₂O)²⁺ (L = L¹ = cyclam and L² = meso-Me-6-cyclam) react with alkyl hydroperoxides RC(CH₃)₂OOH to generate the corresponding rhodium(III) alkyls L(H₂O)RhR²⁺ (R = CH₃, C₂H₅, PhCH₂). Methyl and benzyl complexes can also be prepared by bimolecular group transfer from alkyl cobaloximes (dmgH)₂(H₂O) CoR and (dmgBF₂)₂(H₂O) CoR (R = CH₃, PhCH₂) to LRh(H₂O)²⁺. Moreover, the new complexes were characterized by solution NMR and by crystal structure analysis. They exhibit great stability in aqueous solution at room temperature, but undergo efficient Rh-C bond cleavage upon photolysis.

• Research Organization: Ames Lab., Ames, IA (United States)
• Sponsoring Organization: USDOE Office of Science (SC)
• DOE Contract Number: AC02-07CH11358
• OSTI ID: 1134202
• Report Number(s): IS-J 8213
• Journal Information: Inorganica Chimica Acta, Vol. 409; ISSN 0020-1693
• Publisher: Elsevier
• Country of Publication: United States
• Language: English

Related Subjects

36 MATERIALS SCIENCE
Alkylrhodium
AQUEOUS-SOLUTION
bridged dicobaloximes
crystal-structure
hydrogen-atom transfer
kinetics
nmr
photochemical generation
photochemistry
RADICALS
structure-property relationship
synthesis
thermodynamics
variable-temperature h-1-nmr
x-ray