ENDOR study of bis(acetylacetonato)copper(II) in solid solution

Journal Article · Thu Mar 03 04:00:00 EST 1983 · J. Phys. Chem.; (United States)

DOI:https://doi.org/10.1021/j100228a017· OSTI ID:5556420

Kirste, B; van Willigen, H

The bis(acetylacetonato)copper(II) (Cu(acac)/sub 2/) complex and its adducts with methanol and pyridine in frozen solution have been studied by using ENDOR and electron-nuclear-nuclear triple resonance (TRIPLE). The ENDOR spectra yield the values of the hyperfine tensors of the CH and CH/sub 3/ protons. Signs of the hyperfine components were determined with the aid of TRIPLE and computer simulations. Measurements of quadrupole splittings in /sup 2/H ENDOR spectra of Cu(acac-3-d)/sub 2/ oriented in a frozen liquid crystal allowed the assignment of the in-plane CH couplings to specific molecular axes and also provided information on the alignment of the molecule in the nematic phase. It is shown that TRIPLE can be used to reduce a powder ENDOR spectrum to a single-crystal-type spectrum that can give semiquantitative information on the relative orientation of hyperfine tensor axes. The proton hyperfine interactions in Cu(acac)/sub 2/ are similar to those in VO(acac)/sub 2/, notwithstanding the difference in round-state orbital of the unpaired electron. Adduct formation does not have much effect on the hyperfine components of the CH and CH/sub 3/ protons. The ENDOR data indicate that methanol and pyridine bind in a vacant axial position.

• Research Organization: Univ. of Massachusetts, Boston
• DOE Contract Number: AC02-81ER10911
• OSTI ID: 5556420
• Journal Information: J. Phys. Chem.; (United States), Journal Name: J. Phys. Chem.; (United States) Vol. 87:5; ISSN JPCHA
• Country of Publication: United States
• Language: English

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
400201* -- Chemical & Physicochemical Properties
ACETYLACETONE
ALCOHOLS
AZINES
CHELATING AGENTS
COMPLEXES
COMPUTERIZED SIMULATION
COPPER COMPLEXES
ENDOR
HETEROCYCLIC COMPOUNDS
HYDROXY COMPOUNDS
HYPERFINE STRUCTURE
KETONES
MAGNETIC RESONANCE
METHANOL
ORGANIC COMPOUNDS
ORGANIC NITROGEN COMPOUNDS
ORGANOMETALLIC COMPOUNDS
PYRIDINE
PYRIDINES
REAGENTS
RESONANCE
SIMULATION
TRANSITION ELEMENT COMPLEXES