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13C NMR Shifts As an Indicator of U–C Bond Covalency in Uranium(VI)

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13C NMR Shifts As an Indicator of U–C Bond Covalency in Uranium(VI) Article Cite This: Inorg. Chem. 2019, 58, 4152−4163 pubs.acs.org/IC 13C NMR Shifts as an Indicator of U−C Bond Covalency in Uranium(VI) Acetylide Complexes: An Experimental and Computational Study Kimberly C. Mullane,† Peter Hrobarik,́ *,‡,§ Thibault Cheisson,† Brian C. Manor,† Patrick J. Carroll,† and Eric J. Schelter*,† † P. Roy and Diana T. Vagelos Laboratories, Department of Chemistry, University of Pennsylvania, 231 South 34th Street, Philadelphia, Pennsylvania 19104, United States ‡ Department of Inorganic Chemistry, Faculty of Natural Sciences, Comenius University, SK-84215 Bratislava, Slovakia § Institut für Chemie, Technische Universitaẗ Berlin, Straße des 17. Juni 135, D-10623 Berlin, Germany *S Supporting Information ABSTRACT: A series of uranium(VI)−acetylide complexes of the general VI − − formula U (O)(C C C6H4 R)[N(SiMe3)2]3, with variation of the para substituent (R = NMe2, OMe, Me, Ph, H, Cl) on the aryl(acetylide) ring, was prepared. These compounds were analyzed by 13C NMR spectroscopy, which showed that the acetylide carbon bound to the uranium(VI) center, U−C C−Ar, was shifted strongly downfield, with δ(13C) values ranging from 392.1 to 409.7 ppm for Cl and NMe2 substituted complexes, respectively. These extreme high-frequency 13C resonances are attributed to large negative paramagnetic (σpara) and relativistic spin−orbit (σSO) shielding contributions, associated with extensive U(5f) and C(2s) orbital contributions to the U−C bonding in title complexes. The trend in the 13C chemical shift of the terminal acetylide carbon is opposite that observed in the series of parent (aryl)acetylenes, due to shielding effects of the para substituent. The 13C chemical shifts of the acetylide carbon instead correlate with DFT computed U−C bond lengths and corresponding QTAIM delocalization indices or Wiberg bond orders. SQUID magnetic susceptibility measurements were indicative of the Van Vleck temperature independent paramagnetism (TIP) of the uranium(VI) complexes, suggesting a magnetic field-induced mixing of the singlet ground-state (f0) of the U(VI) ion with low-lying (thermally inaccessible) paramagnetic excited states (involved also in the perturbation-theoretical treatment of the unusually large paramagnetic and SO contributions to the 13C shifts). Thus, together with reported data, we demonstrate that the sensitive 13C from https://pubs.acs.org/doi/10.1021/acs.inorgchem.8b03175. NMR shifts serve as a direct, simple, and accessible measure of uranium(VI)−carbon bond covalency. Downloaded by UNIV OF PENNSYLVANIA at 07:09:47:621 on June 04, 2019 ■ INTRODUCTION with respect to an oxo ligand.10 The axial U−C bond in this compound was short (2.337(14) Å) when compared with Interest in organometallic uranium complexes developed in the − − 1950s for applications in isotope separations processes. equatorial U C bonds, as in the uranyl alkyl complex reported by Hayton and co-workers, [Li- Actinide organometallic complexes were expected to be VI 34 volatile, in analogy with transition metal organometallic (DME)1.5]2[U O2(CH2SiMe3)4] (2.489(6) Å; Figure 1). 1,2 For equatorial U−C interactions with more dative bonding, as complexes. Since that time, a number of uranium(IV) alkyl VI complexes have been synthesized, supported by substituted in U O2Cl[HC(PPh2NMes)2](THF) (Mes = C6H2-2,4,6- − − 3 6 7 10 11 12,13 Me3), reported by Liddle and co-workers, longer bonds of cyclopentadienyl, amide, alkoxide, phosphine, 35 14−17 2.7935(17) Å were observed. When comparing within this and homoleptic ligand frameworks. However, uranium 13 VI alkyl complexes in the oxidation states III,18,19 V,20 and series of compounds, the C NMR spectra of U O2Cl[HC- 10,20,21 (PPh2NMes)2](THF) and 1-H, recorded in benzene-d6 at VI remain relatively scarce. Among the known organo- − metallic uranium complexes are a number of uranium(IV) room temperature, revealed that the chemical shift of the U C − acetylide complexes.22 32 However, as in the chemistry of carbon atom ranged from 7 to 395 ppm, respectively. These chemical shifts indicated that long U−C bonds (2.7935(17) Å) uranium alkyls, there are few examples of uranium acetylides in 13 the other available oxidation states of uranium.10,25,33 had C resonances similar to those of free, diamagnetic − Work from our group recently reported the first example of a ligands, while carbon atoms with short U C bonds (2.337(14) uranium(VI) acetylide complex, UVI(O)(CC−Ph)[N- (SiMe3)2]3 (1-H), stabilized through the inverse trans Received: November 12, 2018 influence by the trans position of the (phenyl)acetylide ligand Published: March 8, 2019 © 2019 American Chemical Society 4152 DOI: 10.1021/acs.inorgchem.8b03175 Inorg. Chem. 2019, 58, 4152−4163 Inorganic Chemistry Article Figure 1. Selected previously reported uranium(VI) organometallic complexes, the experimental U−C bond lengths (in Å), and 13C chemical shifts − 13 VI VI − (in ppm with respect to TMS) of the U C carbon. The C NMR spectra of U O2Cl[HC(PPh2NMes)2](THF) and U (O)(C C 13 VI Ph)[N(SiMe3)2]3 (1-H) were collected at room temperature in benzene-d6. The C NMR spectra of [Li(DME)1.5]2[U O2(CH2SiMe3)4] and VI − − ° 10,20,34,35 U (CH2SiMe3)6 were recorded at 1.6 and 45.5 C, respectively, in THF-d8. Å) were shifted strongly downfield, usually beyond the typical ■ RESULTS AND DISCUSSION 36,37 range of diamagnetic substances (Figure 1). The Synthesis and Characterization of Uranium(VI) VI homoleptic alkyl compound, U (CH2SiMe3)6, reported by (Phenyl)Acetylide Complexes. 1-H fi Previously, compound Hayton and co-workers, has shown the most down eld shifted had been synthesized and reported by our group (Scheme − ° resonance, at 434 ppm, recorded at 46 C in THF-d8, with a 1).10 The synthesis of 1-H was accomplished by reaction of short calculated U−C bond length of 2.335 Å, although no 20,34 crystal structure was obtained (Figure 1). Scheme 1. Synthesis of Uranium(VI) Acetylide Complexes Previously, information about bonding and electronic 1-R (R = NMe , OMe, Me, Ph, H, Cl) structure was obtained by Hrobariḱ and co-workers from 2 correlating experimental and computed 77Se and 125Te chemical shifts of high valent actinide complexes bearing actinide-chalcogen multiple bonds.38 Also, 13C NMR spectros- copy has been used to examine the covalency of U−C bonds in two isolated uranium(VI) complexes, [Li- VI VI 34 (DME)1.5]2[U O2(CH2SiMe3)4]andU(CH2SiMe3)6. NLMO (natural localized molecular orbital) hybridization VI analysis revealed that U (CH2SiMe3)6 had increased the uranium contribution to the U−C bond compared with VI [Li(DME)1.5]2[U O2(CH2SiMe3)4], with metal-based contri- III butions of 28.9 and 21.9%, respectively. This covalency was U [N(SiMe3)2]3 with CuCCPh in a solution of diethyl ether. reflected in the chemical shift of the uranium-bound carbon, This reaction generated the uranium(IV) (phenyl)acetylide fi VI IV which was shifted down eld to 434 ppm for U (CH2SiMe3)6, complex, U (C CPh)[N(SiMe3)2]3. This compound was compared with 243 ppm for [Li- then reacted with N-methylmorpholine N-oxide, an oxygen- VI 20,34 (DME)1.5]2[U O2(CH2SiMe3)4](Figure 1). atom transfer reagent, to yield 1-H as a crystalline solid (59% These data indicated that increased U(VI)−C covalency yield). In order to generate a library of uranium(VI) within structurally related series could be evaluated in the (aryl)acetylide complexes with varying substituents in the extent of the downfield chemical shift in 13CNMR para position, we employed a similar synthetic strategy and spectroscopy. However, only a few examples of uranium(VI) generated 1-R (R = NMe2, OMe, Me, Ph, Cl) complexes in organometallic complexes have been isolated, which prevents low to moderate crystalline yields of 3−28% (Scheme 1). 1H this observation from being further substantiated. Herein, we NMR spectra of crude mixtures showed that 1-R were the present the synthesis and characterization of a series of major products and that the low yields were mainly due to uranium(VI) (aryl)acetylide complexes with varying substitu- isolation; the products were difficult to crystallize due to their VI − − tion in the para position, U (O)(C C C6H4 R)[N- high solubilities in organic solvents. (SiMe3)2]3 (R = NMe2, OMe, Me, Ph, H, Cl; 1-R). These Compounds 1-R (R = NMe2, OMe, Me, Ph, H, Cl) were complexes exhibited extreme downfield chemical shifts of the characterized by X-ray diffraction as well as by 1H and 13C uranium-bound acetylide carbon, U−CC−Ar, ranging from NMR spectroscopies. The 1H NMR spectra appeared within 409.7 to 392.1 ppm. Computed U−C bond lengths and the standard chemical shift window (0−10 ppm), with two sets Quantum Theory of Atoms in Molecules (QTAIM) of aryl peaks, ranging from 7.34 and 6.19 ppm for 1-NMe2 to delocalization indices and Wiberg bond orders were used to 7.15 and 6.88 ppm for 1-Cl. The resonance of methyl protons − 1 determine the extent of U C covalency. QTAIM computa- of N(SiMe3)2 ligands appeared as two peaks in the H NMR tional methods have recently been used to examine actinide− spectra for 1-R complexes due to hindered rotation along the ligand (An−L) bond covalency in a number of reported U−N bond. These peaks ranged from 0.77 and 0.72 ppm for 1- 38−46 1 compounds.
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