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Updated: Aug 30, 2026

Line Shape Analysis of Dynamic NMR Spectra for Characterizing Coordination Sphere Rearrangements at a Chiral Rhenium Polyhydride Complex
Published on: July 27, 2022
Synthesis and characterization of novel rhenium(V) tetradentate N2O2 Schiff base monomer and dimer complexes
Paul D Benny1, Charles L Barnes, Pamela M Piekarski
1The Chemistry Department, University of Missouri, Columbia, Missouri 65211, USA.
Abstract:
Several rhenium(V) oxo complexes with tetradentate N(2)O(2) Schiff base ligands were synthesized and characterized. The general synthetic procedure involved reaction of [NBu(4)][ReOCl(4)] with a tetradentate Schiff base ligand (L(1) = N,N'-ethylenebis(acetylacetoneimine), (acac(2)en) or L(2) = N,N'-propylenebis(acetylacetoneimine) (acac(2)pn)) in ethanol solution to generate complexes of the form trans-ReOX(L) where X = Cl(-), MeO(-), ReO(4)(-), or H(2)O. 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 mu-oxo-Re(2)O(3)(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 (1)H and (13)C 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(OH(2))(acac(2)en)]Cl (H(20)C(12)ClN(2)O(4)Re) 1, triclinic (Ponemacr;), a = 7.2888(6) A, b = 9.8299(8) A, c = 10.8195(9) A, alpha = 81.7670(10) degrees, beta = 77.1510(10) degrees, gamma = 87.6200(10) degrees, V = 747.96(11) A(3), Z = 2; trans-[ReO(OReO(3))(acac(2)en)] (H(18)C(12)N(2)O(7)Re(2)) 2, monoclinic (P2(1)/c), a = 7.5547(4) A, b = 8.7409(5) A, c= 25.7794(13) A, beta = 92.7780(10) degrees, V = 1700.34(16) A(3), Z = 4; trans-[ReOCl(acac(2)pn)] (H(20)C(13)N(2)O(3)ClRe) 3, monoclinic (P2(1)/c), a = 8.1628(5) A, b = 13.0699(8) A, c = 28.3902(17) A, beta = 97.5630(10) degrees, V = 3002.5(3) A(3), Z = 8; trans-[ReO(OMe)(acac(2)pn)] (H(23)C(14)N(2)O(4)Re) 4, monoclinic (P2(1)/c), a = 6.7104(8) A, b = 27.844(3) A, c = 8.2292(9) A, beta = 92.197(2) degrees, V = 1536.4(3) A(3), Z = 4; trans-[mu-oxo-Re(2)O(3)(acac(2)en)(2)] (H(36)C(24)N(4)O(7)Re(2)) 5, monoclinic (P2(1)/n), a = 9.0064(5) A, b = 12.2612(7) A, c = 12.3695(7) A, beta = 90.2853(10) degrees, V = 1365.94(13) A(3), Z = 2; and trans-[mu-oxo Re(2)O(3)(acac(2)pn)(2)] (H(40)C(26)N(4)O(7)Re(2)) 6, monoclinic (P2(1)/n), a = 9.1190(5) A, b = 12.2452(7) A, c = 12.8863(8) A, beta = 92.0510(10) degrees, V = 1438.01(14) A(3), Z = 2.
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