Synthesis and characterization of novel rhenium(V) tetradentate N 2O2 Schiff base monomer and dimer complexes

Paul D. Benny, Charles L. Barnes, Pamela M. Piekarski, John D. Lydon, Silvia S. Jurisson

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Abstract

Several rhenium(V) oxo complexes with tetradentate N2O 2 Schiff base ligands were synthesized and characterized. The general synthetic procedure involved reaction of [NBu4][ReOCl 4] with a tetradentate Schiff base ligand (Li = N,N′ -ethylenebis(acetylacetoneimine), (acac2en) or L2 = N,N′-propylenebis(acetylacetoneimine) (acac2pn)) in ethanol solution to generate complexes of the form trans-ReOX(L) where X = Cl -, MeO-, ReO4-, or H2O. The product isolated from the reaction was found to be dependent on the reaction conditions, in particular the presence or absence of water and/or base. The μ-oxo-Re2O3(L)2 dimers were synthesized and characterized for chemical and structural comparison to the related monomers. Conversion of the monomer to its dimer analogue was followed qualitatively by spectrophotometry. The complexes were characterized by 1H and 13C NMR, UV-vis, and IR spectroscopy, elemental analysis, and single crystal X-ray diffraction. The crystallographic data reported for the structures are as follows: trans-[ReO(OH2)(aca 2en)]Cl (H20C12ClN2O4Re) 1, triclinic (P1), a = 7.2888(6) Å, b = 9.8299(8) Å, c = 10.8195(9) Å, α = 81.7670(10)°, β = 77.1510(10)° γ = 87.6200(10)°, V = 747.96(11) Å3, Z = 2; trans-[ReO(OReO3)(acac2en)] (H18C 12N2O7Re2) 2, monoclinic (P2 1/c), a = 7.5547(4) Å, b = 8.7409(5) Å, c = 25.7794(13) Å, β = 92.7780(10)°, V = 1700.34(16) Å3, Z = 4; trans-[ReOCl(acac2pn)] (H20C13N 2O3ClRe) 3, monoclinic (P21/c), a = 8.1628(5) Å, b = 13.0699(8) Å, c = 28.3902(17) Å, β = 97.5630(10)°, V = 3002.5(3) Å3, Z = 8; trans-[ReO(OMe)(acac2pn)] (H23O14N 2O4Re) 4, monoclinic (P21/c), a = 6.7104(8) Å, b = 27.844(3) Å, c = 8.2292(9) Å, β = 92.197(2)°, V = 1536.4(3) Å3, Z = 4; trans-[μ-oxo-Re2O 3(acac2en)2] (H36O 24N4O7Re2) 5, monoclinic (P2 1/n), a = 9.0064(5) Å, b = 12.2612(7) Å, c = 12.3695(7) Å, β = 90.2853(10)°, V = 1365.94(13) Å3, Z = 2; and trans-[μ-oxo Re2O3(acac2pn) 2] (H40C26N4O7Re 2) 6, monoclinic (P21/n), a = 9.1190(5) Å, b = 12.2452(7) Å, c = 12.8863(8) Å, β = 92.0510(10)°, V = 1438.01(14) Å3, Z = 2.

Original languageEnglish
Pages (from-to)6519-6527
Number of pages9
JournalInorganic Chemistry
Volume42
Issue number20
DOIs
StatePublished - Oct 6 2003
Externally publishedYes

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