<?xml version="1.0" encoding="UTF-8"?><xml><records><record><source-app name="Biblio" version="7.x">Drupal-Biblio</source-app><ref-type>17</ref-type><contributors><authors><author><style face="normal" font="default" size="100%">Pattanayak, Santanu</style></author><author><style face="normal" font="default" size="100%">Jasniewsk, Andrew J.</style></author><author><style face="normal" font="default" size="100%">Rana, Atanu</style></author><author><style face="normal" font="default" size="100%">Draksharapu, Apparao</style></author><author><style face="normal" font="default" size="100%">Singh, Kundan K.</style></author><author><style face="normal" font="default" size="100%">Weitz, Andrew</style></author><author><style face="normal" font="default" size="100%">Hendrich, Michael</style></author><author><style face="normal" font="default" size="100%">Que, Lawrence, Jr.</style></author><author><style face="normal" font="default" size="100%">Dey, Abhishek</style></author><author><style face="normal" font="default" size="100%">Sen Gupta, Sayam</style></author></authors></contributors><titles><title><style face="normal" font="default" size="100%">Spectroscopic and reactivity comparisons of a pair of bTAML complexes with Fe-V=O and Fe-IV=O units</style></title><secondary-title><style face="normal" font="default" size="100%">Inorganic Chemistry</style></secondary-title></titles><dates><year><style  face="normal" font="default" size="100%">2017</style></year><pub-dates><date><style  face="normal" font="default" size="100%">JUN</style></date></pub-dates></dates><volume><style face="normal" font="default" size="100%">56</style></volume><pages><style face="normal" font="default" size="100%">6352-6361</style></pages><language><style face="normal" font="default" size="100%">eng</style></language><abstract><style face="normal" font="default" size="100%">In this report we compare the geometric and electronic structures and reactivities of [Fe-V(O)](-) and [Fe-IV(O)](2-) species supported by the same ancillary nonheme biuret tetraamido macrocyclic ligand (bTAML). Resonance Raman studies show that the Fe-O vibration of the [Fe-IV(O)](2-) complex 2 is at 798 cm(-1), compared to 862 cm(-1) for the corresponding [Fe-V(O)](-) species 3, a 64 cm(-1) frequency difference reasonably reproduced by density functional theory calculations. These values are, respectively, the lowest and the highest frequencies observed thus far for nonheme high-valent Fe-O complexes. Extended X-ray absorption fine structure analysis of 3 reveals an Fe-O bond length of 1.59 angstrom, which is 0.05 angstrom shorter than that found in complex 2. The redox potentials of 2 and 3 are 0.44 V (measured at pH 12) and 1.19 V (measured at pH 7) versus normal hydrogen electrode, respectively, corresponding to the [Fe-IV(O)](2-)/[Fe-III(OH)](2-) and [Fe-V(O)](-)/[Fe-IV(O)](2-) couples. Consistent with its higher potential (even after correcting for the pH difference), 3 oxidizes benzyl alcohol at pH 7 with a second-order rate constant that is 2500-fold bigger than that for 2 at pH 12. Furthermore, 2 exhibits a classical kinteic isotope effect (KIE) of 3 in the oxidation of benzyl alcohol to benzaldehyde versus a nonclassical KIE of 12 for 3, emphasizing the reactivity differences between 2 and 3.</style></abstract><issue><style face="normal" font="default" size="100%">11</style></issue><work-type><style face="normal" font="default" size="100%">Article</style></work-type><custom3><style face="normal" font="default" size="100%">Foreign</style></custom3><custom4><style face="normal" font="default" size="100%">4.82</style></custom4></record></records></xml>