STRUCTURALLY DIVERSE MANGANESE(III) SCHIFF-BASE COMPLEXES - CHAINS, DIMERS, AND CAGES
Cited 143 times inCited 94 times in
- STRUCTURALLY DIVERSE MANGANESE(III) SCHIFF-BASE COMPLEXES - CHAINS, DIMERS, AND CAGES
- BONADIES, JA; KIRK, ML; Lah, Myoung Soo; KESSISSOGLOU, DP; HATFIELD, WE; PECORARO, VL
- Issue Date
- AMER CHEMICAL SOC
- INORGANIC CHEMISTRY, v.28, no.11, pp.2037 - 2044
- Manganese(III) forms a rich variety of complexes with the dianion of the Schiff base ligand N,N′-disalicylidene-2-hydroxypropylenediamine (2-OH-SALPN) and its ring-substituted derivatives. Single crystals of [Mn(2-OH-SALPN)OAc] n (1) are isolated when manganese(III) acetate is reacted with 2-OH-SALPN, in DMF. This infinite chain shows an anti-anti configuration for the bridging acetates. When 1 is dissolved in methanol and 1 equiv of NaOH is added, a dinuclear [Mn III 2(2-OH-SALPN) 2(CH 3OH)]·CH 3OH complex, 3, is isolated. X-ray analysis of crystals of the 5-chloro-2-OH-SALPN derivative 4 show this compound to be a monoalkoxy-bridged species with the longest Mn(III)-Mn(III) separation (3.808 A) yet observed for a discrete single-atom-bridged dimer. If NaOMe is used as a base rather than NaOH, the first example of a totally encapsulated tetrakis(phenolato)-bis(acetato)-caged sodium cation, 5, is isolated. Two Mn III(2-OH-SALPN) units are linked by this sodium ion, forming a bimetallic, trinuclear cluster. The variable-temperature magnetic behavior of these materials shows that spin exchange between the manganese ions is weak or nonexistent [1, J = -1.72 cm -1 and g = 1.97; 4, J = -3.55 cm -1 and g = 1.95; 5, follows Curie-Weiss law behavior with no evident spin exchange between Mn(III) ions (g ∥ = 2.00, g ⊥ = 2.05, D = -6.13 cm -1)]. X-ray crystallographic parameters: 1, C 19H 19N 2O 5Mn, mol wt 410.3, orthorhombic crystal system (Pnma), a = 6.528 (4) A, b = 16.827 (6) A, c= 16.754 (6) A, V = 1840 (1) A 3, Z = 4, 2054 data collected with 0° < 2θ < 50°, 1180 data with I > 3σ(I), R = 0.057, R w = 0.057; 4, C 36H 34N 4O 8Mn 2Cl 4, mol wt 900, monoclinic crystal system (P2 1/c), a = 10.944 (2) A, b = 23.275 (5) A, c = 16.047 (2) A, β = 99.29 (1)°, V = 4034 (1) A 3, Z = 4, 5315 data collected with 0° < 2θ < 45°, 3247 data with I > 2σ(I), R = 0.057, R w = 0.045; 5, C 44H 55N 4O 18Mn 2Na, mol wt 1060, triclinic crystal system (P1), a = 9.434 (5) A, b = 10.436 (4) A, c = 12.758 (8) A, α = 94.42 (4)°, β = 105.50 (4)°, γ = 91.50 (4)°, V = 1205 (1) A 3, Z = 1, 3174 data collected with 0° < 2θ < 45°, 2445 data with I > 3σ(I), R = 0.068, R w = 0.068.
- ; Go to Link
Appears in Collections:
- SNS_Journal Papers
can give you direct access to the published full text of this article. (UNISTARs only)
Show full item record
Items in DSpace are protected by copyright, with all rights reserved, unless otherwise indicated.