TY - JOUR

T1 - Generation of HO• Radical from Hydrogen Peroxide Catalyzed by Aqua Complexes of the Group III Metals [M(H2O)n]3+ (M = Ga, In, Sc,Y, or La): A Theoretical Study

AU - Novikov, A.S.

AU - Kuznetsov, M.L.

AU - Pombeiro, A.J.L.

AU - Bokach, N.A.

AU - Shul'Pin, G.B.

PY - 2013

Y1 - 2013

N2 - The mechanism of the rate-limiting stage of alkanes oxidation with hydrogen peroxide, that is, formation of the hydroxyl radicals, catalyzed by aqua complexes, [M(H2O)n]3+ (1), of the group III metals exhibiting a unique stable non-zero oxidation state (M = Ga, In, Sc, Y, or La) was theoretically studied in detail at the DFT level. The mechanism involves the substitution of a H2O ligand for H2O 2, protolysis of the coordinated H2O2, substitution of another H2O ligand for H2O2, generation of the hydroxyl radical upon the homolytic O-O bond cleavage in the key complex [M(H2O)(n-2)(H2O 2)(OOH)]2+, and closure of the catalytic cycle. The substitution steps proceed via the dissociative mechanism D (M = Ga and Y) or the associative mechanisms A [M = Sc, La, or In (second substitution)] or I a [M = In (first substitution)]. The general catalytic activity of 1 is determined by three main factors, that is, (i) lability of the complexes, (ii) acidity of the metal-bound ligands, and (iii) the H2O 2 activation toward the

AB - The mechanism of the rate-limiting stage of alkanes oxidation with hydrogen peroxide, that is, formation of the hydroxyl radicals, catalyzed by aqua complexes, [M(H2O)n]3+ (1), of the group III metals exhibiting a unique stable non-zero oxidation state (M = Ga, In, Sc, Y, or La) was theoretically studied in detail at the DFT level. The mechanism involves the substitution of a H2O ligand for H2O 2, protolysis of the coordinated H2O2, substitution of another H2O ligand for H2O2, generation of the hydroxyl radical upon the homolytic O-O bond cleavage in the key complex [M(H2O)(n-2)(H2O 2)(OOH)]2+, and closure of the catalytic cycle. The substitution steps proceed via the dissociative mechanism D (M = Ga and Y) or the associative mechanisms A [M = Sc, La, or In (second substitution)] or I a [M = In (first substitution)]. The general catalytic activity of 1 is determined by three main factors, that is, (i) lability of the complexes, (ii) acidity of the metal-bound ligands, and (iii) the H2O 2 activation toward the

U2 - 10.1021/cs400155q

DO - 10.1021/cs400155q

M3 - Article

VL - 3

SP - 1195

EP - 1208

JO - ACS Catalysis

JF - ACS Catalysis

SN - 2155-5435

IS - 6

ER -