Investigation of the Electronic Structure of Mono(1,1′-Diamidoferrocene) Uranium(IV) Complexes

Abstract

The electronic structure of several mono(1,1'diamidoferrocene) uranium complexes (NN R)UX2 (NN R = fc(NR)2, fc = 1,1'-ferrocenediyl, R = SiMe3, Si t BuMe2, SiMe2Ph, X = I, CH2Ph), (NN TBS)UI(OAr) (OAr = 2,6-di-tertbutylphenoxide), and (NN TBS)U(CH2Ph)(OAr) was investigated by electrochemistry, electronic absorption and vibrational spectroscopy, and DFT calculations. Similar metrical parameters were observed for (NN TBS)U(CH2Ph)2 and (NN DMP)U(CH2Ph)2 (and also for the previously reported (NN TMS)UI2(THF), (NN TBS)UI2(THF), and (NN TBS)U(CH2Ph)(OAr)) that translate in similar DFT parameters (bond orders, metal charges) despite some small differences observed by electrochemistry and IR or electronic absorption spectroscopy.

New Benzylpotassium Reagents and Their Utility for the Synthesis of Homoleptic Uranium(IV) Benzyl Derivatives

“…These spectra are reminiscent of those noted for the (NN R )U(CH 2 Ph) 2 (NN R = fc(NR) 2 , fc = 1,1′-ferrocenediyl; R = Si t BuMe 2 , SiMe 3 , SiMe 2 Ph) family recently reported by Diaconescu. 20 Interestingly, lower molar absorptivities are noted in the spectra for 2-o-OMe and 2-o-Picolyl as compared to the rest of the family, perhaps indicating a difference in coordination of these ligands.…”

Lanthanides and actinides: Annual survey of their organometallic chemistry covering the year 2013

“…Scheme 202 illustrates the series of 1,1 -diamidoferrocene uranium complexes which have been the subject of this study. The complexes (NN DMP )UI 2 (THF), (NN DMP )U(CH 2 Ph) 2 , (NN TBS )UI(OAr), and (NN TBS )U(NPh 2 ) 2 were newly prepared in the course of this investigation [165].…”

Near-infrared C-term MCD spectroscopy of octahedral uranium(v) complexes

“…[30][31][32] Computational studies have been widely employed to interrogate electronic structure in uranium chemistry. [33][34][35][36][37][38][39][40][41][42][43][44][45][46][47] EAS is the most widely employed of these methods, due to its broad availability and the insight it can reveal about f-f transitions in the near-infrared (NIR) region, providing a fingerprint of the oxidation states and ligand environments of uranium coordination complexes. While it is extremely useful to probe energy shifts in f-f transitions as a function of ligand perturbation, EAS can suffer from overlapping transitions and vibrational overtone contributions from solvent in the NIR region, resulting in the loss of informationrich fine structure features.…”