Y. Ciringh et al., MULTINUCLEAR PARAMAGNETIC NMR-SPECTRA AND SOLID-STATE X-RAY CRYSTALLOGRAPHIC CHARACTERIZATION OF MANGANESE(III) SCHIFF-BASE COMPLEXES, Inorganic chemistry, 36(22), 1997, pp. 4968-4982
The H-1 NMR spectra of symmetrically substituted paramagnetic [(R,R'-S
ALOPHEN)Mn-III](+) and [(R,R'-SALOPHEN)Mn-III](2)(mu-O) complexes (SAL
OPHEN is 1,3-bis(salicylideneamino)benzene) were obtained. All of the
monomers and dimers yielded well-resolved but isotropically shifted H-
1 NMR spectra. A diamagnetic suppression routine was applied to the H-
1 NMR spectra that allowed observation of all rapidly relaxing resonan
ces. The binding of axial ligands, acetate, methanol, water, and pyrid
ine was also observable by H-1 NMR. Two X-ray crystal structures were
obtained: [(3,3'-17-crown-6-SALOPHEN)Mn-III].(CH3C(O)O). BaTf2 . 2H(2)
O, [9b]-OAc . OAc . BaTf2 . 2H(2)O, crystallized in the triclinic spac
e group P (1) over bar; with a = 10.747(2) Angstrom, b = 12.271(8) Ang
strom, c = 16.206(6) Angstrom, alpha = 106.10(4)degrees, beta = 103.07
(2)degrees, gamma = 106.06(3), and Z = 2, while [(3,3',6,6'-(CH3)(4)-S
ALOPHEN)-Mn-III]PF6 . H2O, [6b]PF6 . H2O, crystallized in the monoclin
ic space group P2(1)/n, with a = 12.465(1) Angstrom, b = 13.366(2) Ang
strom, c = 15.240(1) Angstrom, beta = 103.051(7)degrees, and Z = 2. [9
b]OAc . BaTf2 . 2H(2)O has the Mn(III) center ligated in the axial pos
itions by one oxygen of the acetate group and an oxygen from one SO3CF
3-. The second oxygen of the acetate is bound to the Ba2+ residing in
the crown ether. The water molecule in [6b]PF6 . H2O is O-bound to the
Mn(III) center and also hydrogen bonded to one of the fluorine atoms
of the PF6 counterion, O-F 3.01 Angstrom. H-1 and F-19 NMR spectra rev
ealed that the hydrogen bond in [6b]PF6 . H2O was preserved in CD3OD.