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Title: Structural, spectroscopic, and magnetochemical characterization of the trinuclear vanadium(III) carboxylates [V{sub 3}O(O{sub 2}CR){sub 6}L{sub 3}](ClO{sub 4}) (R = various groups; L = pyridine, 4-picoline, 3,5-lutidine)

Abstract

Synthetic procedures are described that allow access to the [V{sub 3}O(O{sub 2}CR){sub 6}L{sub 3}](ClO{sub 4}) (R = various groups; L = pyridine (py), 4-picoline (pic) or 3,5-lutidine (lut)) family of complexes. Treatment of VCl{sub 3}(THF){sub 3} with NaO{sub 2}- CR (R = Me, Et) in RCO{sub 2}H/py, pic/MeCN, or CH{sub 2}Cl{sub 2} solution followed by addition of NBu{sup n}{sub 4}ClO{sub 4} leads to isolation of [V{sub 3}O(O{sub 2}CR){sub 6}L{sub 3}](ClO{sub 4}) salts in 47-95% yields. A similar procedure for R = C{sub 6}H{sub 5}, C{sub 6}H{sub 5}, C{sub 6}H{sub 4}-p-OMe, C{sub 6}H{sub 3}-m-Me{sub 2}, and C{sub 6}H{sub 4}-p-Cl but omitting addition of NaO{sub 2}CR provides the corresponding benzoate or substituted-benzoate derivatives in 24-56% yields. The X-ray structure of [V{sub 3}O(O{sub 2}CEt){sub 6}(pic){sub 3}](ClO{sub 4}) (4) shows the anion to consist of a [V{sub 3}O]{sup 7+} triangular fragment with a {mu}{sub 3}-O{sup 2-} ion in the V{sub 3} plane; each triangular edge is bridged by two EtCO{sub 2}{sup -} groups in their familiar syn, syn modes, and there is a terminal pic group on each V{sup III} completing distorted octahedral geometries at the metal atoms. The cation has imposed C{sub 2} symmetry (isosceles V{sub 3} triangle), the C{sub 2} axis passingmore » through one V atom and the central {mu}{sub 3}-O atom, but has D{sub 3h} virtual symmetry (equilateral V{sub 3} triangle). Complex 4 crystallizes in monoclinic space group. Variable-temperature, solid-state magnetic susceptibility measurements were made on complex 1 in the 5.01-280 K region in a 1 kG magnetic field. The effective magnetic moment ({mu}{sub eff}) per V{sub 3} unit decreases gradually from 4.64 {mu}{sub B} at 280 K to 1.76 {mu}{sub B} at 5.01 K.« less

Authors:
; ;  [1]
  1. Indiana Univ., Bloomington, IN (United States); and others
Publication Date:
OSTI Identifier:
476846
Resource Type:
Journal Article
Journal Name:
Inorganic Chemistry
Additional Journal Information:
Journal Volume: 35; Journal Issue: 15; Other Information: PBD: 17 Jul 1996
Country of Publication:
United States
Language:
English
Subject:
40 CHEMISTRY; VANADIUM COMPLEXES; MAGNETIC SUSCEPTIBILITY; CRYSTAL STRUCTURE; MONOCLINIC LATTICES; CHEMICAL PREPARATION; CHEMICAL REACTION YIELD; X-RAY DIFFRACTION; MAGNETIC MOMENTS; GROUND STATES; MATHEMATICAL MODELS

Citation Formats

Castro, S L, Streib, W E, and Sun, Jui-Sui. Structural, spectroscopic, and magnetochemical characterization of the trinuclear vanadium(III) carboxylates [V{sub 3}O(O{sub 2}CR){sub 6}L{sub 3}](ClO{sub 4}) (R = various groups; L = pyridine, 4-picoline, 3,5-lutidine). United States: N. p., 1996. Web. doi:10.1021/ic9602153.
Castro, S L, Streib, W E, & Sun, Jui-Sui. Structural, spectroscopic, and magnetochemical characterization of the trinuclear vanadium(III) carboxylates [V{sub 3}O(O{sub 2}CR){sub 6}L{sub 3}](ClO{sub 4}) (R = various groups; L = pyridine, 4-picoline, 3,5-lutidine). United States. https://doi.org/10.1021/ic9602153
Castro, S L, Streib, W E, and Sun, Jui-Sui. Wed . "Structural, spectroscopic, and magnetochemical characterization of the trinuclear vanadium(III) carboxylates [V{sub 3}O(O{sub 2}CR){sub 6}L{sub 3}](ClO{sub 4}) (R = various groups; L = pyridine, 4-picoline, 3,5-lutidine)". United States. https://doi.org/10.1021/ic9602153.
@article{osti_476846,
title = {Structural, spectroscopic, and magnetochemical characterization of the trinuclear vanadium(III) carboxylates [V{sub 3}O(O{sub 2}CR){sub 6}L{sub 3}](ClO{sub 4}) (R = various groups; L = pyridine, 4-picoline, 3,5-lutidine)},
author = {Castro, S L and Streib, W E and Sun, Jui-Sui},
abstractNote = {Synthetic procedures are described that allow access to the [V{sub 3}O(O{sub 2}CR){sub 6}L{sub 3}](ClO{sub 4}) (R = various groups; L = pyridine (py), 4-picoline (pic) or 3,5-lutidine (lut)) family of complexes. Treatment of VCl{sub 3}(THF){sub 3} with NaO{sub 2}- CR (R = Me, Et) in RCO{sub 2}H/py, pic/MeCN, or CH{sub 2}Cl{sub 2} solution followed by addition of NBu{sup n}{sub 4}ClO{sub 4} leads to isolation of [V{sub 3}O(O{sub 2}CR){sub 6}L{sub 3}](ClO{sub 4}) salts in 47-95% yields. A similar procedure for R = C{sub 6}H{sub 5}, C{sub 6}H{sub 5}, C{sub 6}H{sub 4}-p-OMe, C{sub 6}H{sub 3}-m-Me{sub 2}, and C{sub 6}H{sub 4}-p-Cl but omitting addition of NaO{sub 2}CR provides the corresponding benzoate or substituted-benzoate derivatives in 24-56% yields. The X-ray structure of [V{sub 3}O(O{sub 2}CEt){sub 6}(pic){sub 3}](ClO{sub 4}) (4) shows the anion to consist of a [V{sub 3}O]{sup 7+} triangular fragment with a {mu}{sub 3}-O{sup 2-} ion in the V{sub 3} plane; each triangular edge is bridged by two EtCO{sub 2}{sup -} groups in their familiar syn, syn modes, and there is a terminal pic group on each V{sup III} completing distorted octahedral geometries at the metal atoms. The cation has imposed C{sub 2} symmetry (isosceles V{sub 3} triangle), the C{sub 2} axis passing through one V atom and the central {mu}{sub 3}-O atom, but has D{sub 3h} virtual symmetry (equilateral V{sub 3} triangle). Complex 4 crystallizes in monoclinic space group. Variable-temperature, solid-state magnetic susceptibility measurements were made on complex 1 in the 5.01-280 K region in a 1 kG magnetic field. The effective magnetic moment ({mu}{sub eff}) per V{sub 3} unit decreases gradually from 4.64 {mu}{sub B} at 280 K to 1.76 {mu}{sub B} at 5.01 K.},
doi = {10.1021/ic9602153},
url = {https://www.osti.gov/biblio/476846}, journal = {Inorganic Chemistry},
number = 15,
volume = 35,
place = {United States},
year = {1996},
month = {7}
}