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

Journal Article · Tue Jan 05 23:00:00 EST 1993 · Inorganic Chemistry; (United States)

DOI:https://doi.org/10.1021/ic00053a014· OSTI ID:6837428

Horwitz, C P; Winslow, P J; Warden, J T ^[1]; Lisek, C A ^[2]

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1. Rensselaer Polytechnic Inst., Troy, NY (United States)
2. Monsanto Co., St. Louis, MO (United States)

The Schiff-base complexes (X-SALPRN)Mn[sup II] [X = H, 5-Cl, 5-CH[sub 3]O; SALPRN = 1,3-bis(salicylideneamino)propane] were reacted with dioxygen in CH[sub 3]CN and CH[sub 2]Cl[sub 2]. Mn(IV), and Mn(IV) bis([mu]-oxo) dimers [(X-SALPRN)Mn[sup IV]([mu]-O)][sub 2][X = H (1), 5-Cl (2), 5-CH[sub 3]O (3)] were isolated in high yields and as the sole products from oxygenation in CH[sub 3]CN, but two products were isolated when the oxygenation was performed in CH[sub 2]Cl[sub 2]. One product was the bis([mu]-oxo) dimer, while the second was a green compound formulated as [l brace][(X-SALPRN)Mn[sup III]][sub 2]O[r brace][sub x], where x = 1 or 2 [X = H (4), 5-Cl (5), 5-CH[sub 3]O (6)]. These green compounds formed by reaction of 1-3 with its appropriate Mn(II) complex in a 1:2 ratio. The bis([mu]-oxo) dimers each exhibited a single, reversible one-electron couple E[sup o][sub 1] = [minus]480 mV, E[sup o][sub 2] = [minus]340 mV, and E[sup o][sub 3] = [minus]590 mV all vs SSCE. All of the green compounds exhibited two redox processes, both of which were multielectron and transfer reactions. The ESR spectrum of a frozen solution of the mixed-valence form of 1 observed at 6 K showed the presence of an antiferromagnetically coupled S = [1/2] system with the following best fit parameters: g[sub x] = 2.0092, g[sub y] = 2.0061, g[sub z] = 1.9925; A[sub 1x] = 492 MHz, A[sub 1y] = 448 MHz, A[sub 1z] = 385 MHz, A[sub 2x] = 231 MHz, A[sub 2y] = 227 MHz, A[sub 2x] = 209 MHz. A complete intermetal oxygen atom transfer reaction for compound 4 was observed to occur with (SALEN)Fe[sup II] [SALEN = 1,2-bis(salicylideneamino)ethane] resulting in formation of the (SALPRN)Mn[sup II] and [(SALEN)Fe[sup III]][sub 2]([mu]-O) (7), both in quantitative yield. 53 refs., 4 figs., 1 tab.

• OSTI ID: 6837428
• Journal Information: Inorganic Chemistry; (United States), Journal Name: Inorganic Chemistry; (United States) Vol. 32:1; ISSN 0020-1669; ISSN INOCAJ
• Country of Publication: United States
• Language: English

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
400201* -- Chemical & Physicochemical Properties
CHEMICAL REACTIONS
CHEMISTRY
COMPLEXES
DATA
ELECTROCHEMISTRY
ELECTRON SPIN RESONANCE
ELEMENTS
EXPERIMENTAL DATA
IMINES
INFORMATION
MAGNETIC RESONANCE
MANGANESE COMPLEXES
NONMETALS
NUMERICAL DATA
ORGANIC COMPOUNDS
ORGANIC NITROGEN COMPOUNDS
OXIDATION
OXYGEN
REDUCTION
RESONANCE
SCHIFF BASES
TRANSITION ELEMENT COMPLEXES