Products from reactions of [Mn[sub 2]O[sub 2](O[sub 2]CCH[sub 3])(tpen)][sup 2+] in acidic and neutral aqueous media: [Mn[sub 2]([mu]-O)[sub 2]([mu]-O[sub 2]CCH[sub 3])(tpen)][sup 3+] and [[l brace]Mn[sub 3]([mu]-O)[sub 4](OH)(tpen)[r brace][sub 2]([mu]-tpen)][sup 6+]
- Univ. of California, Berkeley (United States)
The mixed-valence compound [Mn[sub 2]([mu]-O)[sub 2]([mu]-O[sub 2]CCH[sub 3])(tpen)](ClO[sub 4])[sub 2][center dot]3H[sub 2]O (2[center dot]3H[sub 2]O) reacts to form [Mn[sub 2]([mu]-O)[sub 2]([mu]-O[sub 2]CCH[sub 3])(tpen)](ClO[sub 4])[sub 3] (3) is acidic aqueous solution and in contrast is converted to [[l brace]Mn[sub 3]([mu]-O)[sub 4](OH)(tpen)[r brace][sub 2]([mu]-tpen)](ClO[sub 4])[sub 6][center dot]4H[sub 2]O (4[center dot]4H[sub 2]O) in distilled water (tpen is N,N,N[prime],N[prime]-tetrakis(2-pyridylmethyl)-1,2-ethanediamine). Both reactions were carried out in the presence of a large excess of perchlorate counterion. Syntheses, structures, and selected properties of 3 and 4 are reported. Structural parameters for 3 are consistent with both manganese ions being in the 4+ oxidation state. The cyclic voltammogram of 3 in CH[sub 3]CN exhibits IV,IV/IV,III and IV,III/III,III reductions at +0.90 and [minus]0.13 V, respectively, vs SSCE. The cation in 4 resides on an inversion center. Bond distances and angles in 4 confirm that all Mn atoms are in the +4 oxidation state. The structure of 4 consists of two [l brace]Mn[sub 3]O[sub 4][r brace][sup 4+] units linked by one tpen moiety. The [l brace]Mn[sub 3]O[sub 4][r brace][sup 4+] cores in 4 are distorted in a manner that is reminiscent of [Mn[sub 3]O[sub 4](OH)(bpea)[sub 3]][sup 3+] (J. Am. Chem. Soc. 1992, 114, 6398-6406). The cyclic voltammogram of 4 in CH[sub 3]CN displays two irreversible reduction responses at +0.10 and [minus]0.27 V vs SSCE. The EPR spectrum of 4[center dot]4H[sub 2]O in frozen CH[sub 3]CN-C[sub 6]H[sub 5]CH[sub 3] is consistent with an S = 3/2 ground-state origin. Both 3 and 4[center dot]4H[sub 2]O were also characterized by infrared and electronic spectral measurements. 27 refs., 3 figs., 5 tabs.
- OSTI ID:
- 6717649
- Journal Information:
- Inorganic Chemistry; (United States), Journal Name: Inorganic Chemistry; (United States) Vol. 31:26; ISSN 0020-1669; ISSN INOCAJ
- Country of Publication:
- United States
- Language:
- English
Similar Records
Reaction of the Schiff-base complexes (X-SALPRN)Mn[sup II] [X = H, 5-Cl, 5-CH[sub 3]O; SALPRN = 1,3-bis(salicylideneamino)propane] with dioxygen and reactivity of the oxygenated products
Synthesis and structural characterization of the trinuclear mixed-valence complex [[l brace](tiptacn)Mo[sup V]O([mu]-O)[sub 2][r brace][sub 2]Mo[sup IV](bpy)](PF[sub 6])[sub 2][center dot]0. 25CH[sub 3]NO[sub 2] (tiptacn = 1,4,7-tris(2-propyl)-1,4,7-triazacyclononane)
Related Subjects
400201* -- Chemical & Physicochemical Properties
ACETATES
BOND ANGLE
BOND LENGTHS
CARBOXYLIC ACID SALTS
CATIONS
CHALCOGENIDES
CHARGE STATES
CHARGED PARTICLES
CHELATES
CHEMICAL PREPARATION
CHEMICAL REACTIONS
COMPLEXES
CRYSTAL STRUCTURE
DIMENSIONS
ELECTRON SPIN RESONANCE
HYDROGEN COMPOUNDS
HYDROXIDES
IONS
LATTICE PARAMETERS
LENGTH
MAGNETIC RESONANCE
MANGANESE COMPLEXES
MANGANESE COMPOUNDS
MANGANESE OXIDES
OXIDES
OXYGEN COMPOUNDS
PH VALUE
RESONANCE
SYNTHESIS
TRANSITION ELEMENT COMPLEXES
TRANSITION ELEMENT COMPOUNDS
VOLTAMETRY