DOI: 10.1002/chem.201303095

Synthesis of Terminal Uranium(IV) Disulfido and Diselenido Compounds by Activation of Elemental Sulfur and Selenium Ellen M. Matson,[a] Mitchell D. Goshert,[b] John J. Kiernicki,[a] Brian S. Newell,[c] Phillip E. Fanwick,[a] Matthew P. Shores,*[c] Justin R. Walensky,*[b] and Suzanne C. Bart*[a] The interaction between transition metals and chalcogenides has long been an area of interest due to their relevance in industrial[1] and biological[2, 3] applications. More recently, the study of actinide complexes containing these soft donor ligands has been ignited due to their bonding properties, as they offer a convenient platform to explore covalent bonding interactions.[4] These species are typically made by activation of organochalcogenides, including EPPh3 (E=S, Se),[5–8] TePACHTUNGRE(nBu)3,[5] and PhEEPh (E=S, Se, Te),[9–17] by lowvalent uranium. Synthesis of uranium compounds derived from elemental sulfur and selenium has been demonstrated in the formation of bridging species.[7, 8, 12] In many of these examples, two uraniumACHTUNGRE(III) or two uranium(V) centers each contribute one electron to generate uranium(IV) or uranium(VI) dimers by two electron activation of sulfur or selenium. However, in the case of trivalent UACHTUNGRE(H2C=PPh3)(NACHTUNGRE(SiMe3)2)3, the presence of the ylide prevents formation of the bridging species upon activation of elemental sulfur and selenium, resulting in the terminal sulfido and selenido monomers, [Ph3PCH3][U(E)(NACHTUNGRE(SiMe3)2)3].[18] Two electron activation of S8 and Se at a single uranium center has been shown by Hayton and co-workers in the synthesis of the terminal sulfur and selenium-substituted uranyl analogues, [Cp*2Co] [U(O)(E)(NACHTUNGRE(SiMe3)2)3], which is facilitated by an electronrich uranium(IV) species.[19] In contrast to this multi-electron chemistry, little is known about the reactivity of elemental chalcogens with uranium alkyls. Evans has recently demonstrated elemental sulfur insertion into the uranium carbon bonds of tetravalent (h5 :h2-

[a] E. M. Matson, J. J. Kiernicki, P. E. Fanwick, Prof. S. C. Bart H. C. Brown Laboratory, Department of Chemistry Purdue University, West Lafayette, IN 47907 (USA) E-mail: [email protected] [b] M. D. Goshert, Prof. J. R. Walensky Department of Chemistry, University of Missouri Columbia, MO 65211 (USA) E-mail: [email protected] [c] B. S. Newell, Prof. M. P. Shores Department of Chemistry, Colorado State University Fort Collins, CO 80523 (USA) E-mail: [email protected] Supporting information for this article is available on the WWW under http://dx.doi.org/10.1002/chem.201303095.

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C5Me4SiMe2CH2)2U, forming the tethered (tetramethylcyclopentadienyl)dimethylsilyl alkyl disulfido, (h5 :h2[20] C5Me4SiMe2CH2S2)2U. Thus, we set out to study the reactivity of elemental sulfur and selenium with Tp*2UACHTUNGRE(CH2Ph) (1) (Tp* = hydrotris(3,5-dimethylpyrazolyl)borate), as activation could occur either by insertion into the U C bond, by analogy to the work of Evans, or by two electron reduction of the chalcogen. The latter mode of reactivity has been observed for 1 with organoazides[21] and diazomethanes,[22] producing uranium(IV) imido and hydrazonido derivatives, respectively, by extrusion of bibenzyl. Herein we present the reactivity of 1 toward elemental sulfur and selenium, spectroscopic, magnetic, and crystallographic characterization of the products, as well as a computational analysis of the uranium–chalcogenide bonding. The addition of 1/4 equiv of S8 to a green, THF solution of 1 results in an instantaneous color change to yellowbrown [Eq. (1)]. Analysis by 1H NMR spectroscopy revealed

a paramagnetic product with ten broad resonances ranging from 48.93 to 47.97 ppm, consistent with pairwise equivalence in solution. A sharp signal at 2.78 ppm assigned to bibenzyl indicates extrusion of the benzyl group and formation of the uranium(IV) disulfido, Tp*2UACHTUNGRE(h2-S2) (2). Compound 1 displays analogous reactivity with two equivalents of elemental selenium. The 1H NMR spectrum of this product is paramagnetically broadened and shifted, similarly to that of 2, suggesting formation of the diselenido congener, Tp*2UACHTUNGRE(h2-Se2) (3) [Eq. (1)]. Characterization of 2 and 3 by

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COMMUNICATION electronic absorption spectroscopy confirms the + 4 oxidation state of uranium with the presence of sharp but weak transitions in the near infrared regions of the spectra (Figure S1 in the Supporting Information).[23–27] These are consistent with UIV centers, as would be expected for dianionic h2disulfido and h2-diselenido ligands. To definitively determine the solid-state structure of 2, yellow crystals grown from a concentrated THF solution layered with pentane (1:2 ratio) were analyzed by single crystal X-ray diffraction. Refinement of the data shows an eight coordinate, dodecahedral uranium center with two Tp* ligands and an S2 fragment coordinated in an h2-fashion (Figure 1, left and Table 1). The U N(pz) distances are con-

Figure 1. Molecular structure of 2 (left) and 3 (right) shown with 30 % probability ellipsoids. Hydrogen atoms and solvent molecules have been removed for clarity.

sistent with those previously reported for uranium(IV) bis(hydrotris(3,5-dimethylpyrazolyl)borate) species.[21, 28] The U S distances of 2.628(2) and 2.6214(19)  are the same within error, and within the range of UIV thiolates (2.588 to 2.736 ), supporting anionic interactions between sulfur and uranium.[10, 29, 30] The U S bonds in 2 are also similar to UVI terminal disulfido compounds,[31–33] including ACHTUNGRE[(n-C3H7)2NH2]2ACHTUNGRE[(UO2)ACHTUNGRE((n-C3H7)2NCOS)2ACHTUNGRE(h2-S2)], which has distances of 2.711(3) and 2.873(2) , and the uranyl persulfido, Na4ACHTUNGRE[(UO2)ACHTUNGRE(h2-S2)3ACHTUNGRE(CH3OH)8,[34] with distances ranging from 2.751(1) to 2.796(1) . The S S bond of 2.075(3)  in 2 is within error of that reported for [(n-C3H7)2NH2]2ACHTUNGRE[(UO2)ACHTUNGRE((n-C3H7)2NCOS)2ACHTUNGRE(h2-S2)] (2.05(1) ) and similar to those for Na4ACHTUNGRE[(UO2)ACHTUNGRE(h2-S2)3]ACHTUNGRE(CH3OH)8 (2.077(2) to 2.082(2) ) as well as other terminal disulfido complexes for uranium (2.077(2) to 2.09(1) )[31–33] and transition metals (2.010 to 2.072 ),[35–39] supporting the formation of the S22 moiety. The uranium(IV) bridging disulfido, [(R2N)3U]2(m-h2 :h2-S2), synthesized by Hayton and co-workers has U S distances ranging from 2.7062(16) to 2.9228(15)  and an S S distance of 2.1051(19) , slightly longer than that observed for 2 most likely due to its dimeric nature.[8]

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Due to the paucity of terminal diselenido species, X-ray crystallographic characterization was performed on single crystals of 3 grown from a concentrated THF solution layered with diethyl ether (1:2 solvent ratio). Refinement of the data showed an analogous structure to 2 (Figure 1, right, and Table 1). The U Se distances of 2.8147(5) and Table 1. Comparison of experimental and calculated bond distances [] for 2 and 3. Bond

2, E=S

Calcd

3, E=Se

Calcd

U1 U1 U1 U1 U1 U1 U1 U1 E1

2.687(7) 2.520(6) 2.619(6) 2.518(6) 2.676(6) 2.648(6) 2.628(2) 2.6214(19) 2.075(3)

2.810 2.553 2.690 2.550 2.732 2.746 2.644 2.628 2.118

2.559(4) 2.660(4) 2.531(4) 2.664(4) 2.589(4) 2.506(4) 2.8147(5) 2.7745(5) 2.3394(7)

2.739 2.545 2.751 2.555 2.838 2.693 2.811 2.795 2.375

N11 N21 N31 N61 N71 N81 E1 E2 E2

2.7745(5)  compare favorably to Cp*2UACHTUNGRE(SePh)2 (2.7997(7) and 2.8011(7) )[11] and Cp*2U(Me)ACHTUNGRE(SePh) (2.8432(7) ).[10] The Se1 Se2 distance of 2.3394(7)  is between those reported for [UACHTUNGRE(NtBu)2IACHTUNGRE(tBu2bpy)]2(m-h2 :h2-Se4) of 2.2756(10) and 2.4152(14) ,[12] and is slightly shorter than those reported for K4USe8 of 2.385(4) and 2.401(4) .[40] The Se22 moiety in 3 is similar to terminal diselenido transition metal complexes,[41–45] and again represents a rare example of a diACHTUNGREselenido ligand formed by uranium activation of selenium. Investigation into the vibrational properties of 2 and 3 shows the characteristic inequivalent B H absorptions for the bis-Tp* ligand framework by IR spectroscopy.[21] Additionally, compound 2 possesses an absorption at 508 cm 1 assigned as the uACHTUNGRE(S S) stretching frequency characteristic of an S22 ligand, which was absent in 3. Similar stretches (510– 530 cm 1) were assigned for [(n-C3H7)2NH2]2ACHTUNGRE[(UO2)ACHTUNGRE((nC3H7)2NCOS)2ACHTUNGRE(h2-S2)].[35] The Raman spectrum of 3 displays intense absorbances from 600–1600 cm 1 assignable to the Tp* ligands,[46] with a weak absorption in the far-infrared region (298 cm 1) assigned to uACHTUNGRE(Se Se). This absorption, which is similar to those found in [MACHTUNGRE(h2-Se2)(L)2]Cl (M=Ir, Rh; L=dppe, dmpe),[41] confirms the Se22 assignment for 3. Compounds 2 and 3 are rare examples of uranium(IV) terminal disulfido and diselenido species made by activation of elemental chalcogens. Their formation is due in part to the facile homolytic cleavage of the U C bond in 1, as well as the driving force to attain the thermodynamically stable + 4 oxidation state and difficulty in creating terminal uraniACHTUNGREum(IV) sulfur multiple bonds. The only example, [Na([18]crown-6)][UACHTUNGRE(Cp*)2ACHTUNGRE(StBu)(S)], was synthesized by Ephritikhine in 1999.[47] Interestingly, the products of sulfur and selenium insertion into the uranium carbon bond of 1 were not isolated by analogy to (h5 :h2-C5Me4SiMe2CH2S2)2U.[20] There are relatively few reports of uranium alkyl complexes with S8 and Se, however, it was shown that treating Cp*2UACHTUNGRE(CH3)2 with two equivalents of PhEEPh (E=S, Se, Te) produces

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Cp*2UACHTUNGRE(EPh)2 with loss of 2 MeEPh, whereas using one equivalent of PhTeTePh generates Cp*2UACHTUNGRE(TeC6H4) by CH4 and MeTePh extrusion.[10] Full geometry optimizations were performed on complexes 2 and 3 at the B3LYP level of theory and frequency calculations showed that the global minima were reached in both cases. Using a basis set without d functions the uranium chalcogenide bond distances were elongated by approximately 0.05 , which is typical for B3LYP functional, but the E E bond distances were lengthened over 0.15 . Thus, distances are reported using the 6-311G* basis set, which reproduced the bond distances to within 0.05  of the experimentally determined values (Table 1). Mulliken spin densities are 2.202 and 2.260 for 2 and 3, respectively, indicating the presence of two unpaired electrons centered on uranium. The extra spin density is due to the donation from the nitrogen atoms from the Tp* ligands and (E2)2 moiety. To this point, the spin densities of each sulfur atom in 2 are 0.4647 and 0.5109, respectively, whereas the spin densities of each selenium atom in 3 are 0.3767 and 0.4260, respectively. This indicates a greater uranium sulfur interaction than uranium selenium. The bonding orbitals between uranium and each dichalcogenide moiety are found in the HOMO to HOMO 3 orbitals with similar Mulliken populations and orbital energies (Table 2 for 2 and Table 3 for 3). Table 2. Mulliken populations and orbital energies for 2. Orbital HOMO HOMO 1 HOMO 2 HOMO 3

Energy [eV] 0.171 0.202 0.209 0.220

d

f

S 3p

Total

Type

0.05 0.02 0.04 0.05

0.11 0.80 0.72 0.34

0.77 0.05 0.18 0.41

0.16 0.82 0.76 0.39

pACHTUNGRE(d+f) unpaired e unpaired e sACHTUNGRE(d+f)

Table 3. Mulliken populations and orbital energies for 3. Orbital HOMO HOMO 1 HOMO 2 HOMO 3

Energy [eV] 0.161 0.200 0.205 0.212

d

f

Se 4p

Total

Type

0.05 0.11 0.02 0.00

0.18 0.18 0.80 0.93

0.72 0.62 0.11 0.00

0.23 0.29 0.82 0.93

pACHTUNGRE(d+f) sACHTUNGRE(d+f) unpaired e unpaired e

Complex 2 contains two unpaired electrons in the HOMO 1 and HOMO 2 with 82 and 76 % total uraniumbased contribution, respectively (Figure 2). Substantial donation from S 3p orbitals are observed in the HOMO (77 %) and HOMO 3 (41 %) with smaller uranium character of 11 % 5f and 5 % 6d for the HOMO. A p interaction is observed for the HOMO whereas the HOMO 3 contains a sbond. Interestingly, the HOMO 3 features 34 % U 5f and 5 % U 6d contributions, which is high for a UIV complex but this has been observed previously using the B3LYP functional.[48] One reason for this large uranium character could be energy level matching, or degeneracy, between the U 5f and S 3p orbitals.[49–51] This has been shown to produce more covalent bonds with 2p orbitals of carbon and nitrogen, but

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Figure 2. Tp*2UACHTUNGRE(h2-S2): a) HOMO, b) HOMO 1, c) HOMO 2, and d) HOMO 3 of 2 are shown. Plotted at the 0.030 isolevel.

the S 3p orbitals would be higher in energy, similarly to the U 5f orbitals. The question of whether the high percentage of actinide character in bonding versus bond strength remains an open debate in 5f element chemistry.[52] In 3, the two unpaired electrons are housed in the HOMO 2 and HOMO 3 orbitals showing 82 and 93 % total uranium character, respectively (Figure 3). The HOMO reveals a p interaction in which uranium 5f (18 %) and 6d (5 %) orbitals interact with each Se 4p (72 % total). The HOMO 1 shows a s-interaction between a Se 4p (62 %) and a combination of U 5f (18 %) and 6d (11 %). In both 2 and 3, the large contributions from S and Se np orbitals indicate a highly polarized, primarily ionic bond between uranium and each (E2)2 fragment. This bonding description is supported by the uranium element bond distances when comparing the sum of the covalent radii: uranium and sulfur sum to 2.44 , whereas uranium and selenium sum to 2.58 . Both values are shorter than the average observed bond distances in the solid-state structures of 2.625 and 2.795  for U S and U Se, respectively. The difference between these values is also similar to the 0.14  change in covalent radii from sulfur to selenium, thus pointing to similar bonding patterns between 2 and 3. Compounds 2 and 3 were analyzed by variable temperature SQUID magnetometry on several independently synthesized solid samples (Figure 4). The high temperature effective magnetic moment for complex 2 is meff = 3.34(1) mB (295 K) and for complex 3 is meff = 2.98 mB (295 K). The room temperature moments are somewhat lower than the

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Terminal Uranium(IV) Disulfido and Diselenido Compounds

COMMUNICATION spin density on S than Se, as was established computationally, but could also be from differences in temperature-independent paramagnetism, spin-orbit coupling and/or ligand distortion. Below 75 K, meff values drop smoothly but more precipitously to 1.04 and 0.94 mB (4 K), respectively. As with other UIV complexes, sizable spin-orbit coupling leads to “non-magnetic” orbital singlet ground states.[58] The synthesis of terminal uranium(IV) disulfido (2) and diselenido (3) compounds was achieved by bibenzyl extrusion from Tp*2UCH2Ph. This work marks a rare example in which such moieties have been generated from exposure to elemental sulfur and selenium. Spectroscopic and single crystal X-ray crystallographic techniques combined support formation of the E22 ligand, whereas magnetic measurements of 2 and 3 show typical temperature dependencies for uranium(IV) derivatives. Density functional calculations show a highly polarized bond between uranium and corresponding chalcogenides, but the deviation of the spin density from 2.000 can be attributed to a small degree of covalent bonding. These studies highlight the unique structure and bonding of rare terminal dichalcogenido uranium(IV) complexes.

Experimental Section Figure 3. Tp*2UACHTUNGRE(h2-Se2): a) HOMO, b) HOMO 1, c) HOMO 2, and d) HOMO 3 of 3 are shown. Plotted at the 0.030 isolevel.

Figure 4. Variable temperature effective magnetic moment data for 2 and 3.

3.58 mB value expected for a 5f2 system (3H4),[53, 54] but well in the range of other reported UIV complexes.[23, 55–58] These species show qualitatively similar temperature-dependent magnetic behavior expected for UIV complexes.[23, 55–58] Decreasing from room temperature to approximately 75 K, the effective magnetic moments decrease slightly for 2 and 3 to 2.64 and 2.40 mB, respectively. The steeper slope observed for 2 versus 3 may be attributable to the greater amount of

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Preparation of Tp*2U(S2) (2): A scintillation vial (20 mL) was charged with 1 (0.050 g, 0.055 mmol) and THF (~ 3 mL). With vigorous stirring 1 =4 equiv of S8 (0.004 g, 0.016 mmol) was weighed by difference and added, resulting in a color change to brown. After 10 min of stirring, solvents were removed under reduced pressure. The product, Tp*2UACHTUNGRE(h2-S2), was recrystallized as a yellow powder from a concentrated THF solution layered with pentane (2:1; 0.032 g, 0.033 mmol, 60 %). 1H NMR (300 MHz, [D6]benzene, 22 8C): d = 48.93 (160, 6 H, Tp*-CH3), 18.31 (199, 2 H, B-H), 14.57 (83, 6 H, Tp*-CH3), 4.78 (93, 2 H, Tp*-CH), 4.26 (93, 6 H, Tp*-CH3), 3.17 (168, 6 H, Tp*-CH3), 2.59 (114, 2 H, Tp*-CH), 0.71 (96, 6 H, Tp*-CH3), 26.64 (74, 2 H, Tp*-CH), 47.97 ppm (90, 6 H, Tp*-CH3); IR (KBr): v˜ = 508 (S S), 2518, 2557 cm 1 (B H); elemental analysis calcd for C30H44N12B2S2U1: C 40.19, H 4.95, N 18.75; found: C 40.19, H 5.08, N 18.69 Preparation of Tp*2UACHTUNGRE(Se2) (3): A scintillation vial (20 mL) was charged with 1 (0.050 g, 0.054 mmol) and THF (~ 5 mL). With vigorous stirring, 2 equiv of Se (0.009 g, 0.114 mmol) were weighed by difference and added. After 30 min, a color change from green to red-brown was observed. Solvents were removed in vacuo. The product, Tp*2UACHTUNGRE(h2-Se2) was isolated as a red-brown powder by washing the resulting residue with diethyl ether (0.052 g, 0.048 mmol, 89 %). Crystals suitable for X-ray analysis were grown from a concentrated THF and pentane solution (2:1 ratio). 1H NMR (300 MHz, [D6]benzene, 22 8C): d = 46.18 (63, 6 H, Tp*CH3), 18.01 (259, 2 H, B-H), 13.90 (40, 6 H, Tp*-CH3), 7.88 (40, 6 H, Tp*-CH3), 4.46 (37, 2 H, Tp*-CH), 2.45 (53, 6 H, Tp*-CH3), 1.12 (36, 2 H, Tp*-CH), 0.05 (37, 6 H, Tp*-CH3), 25.14 (41, 2 H, Tp*-CH), 46.38 ppm (51, 6 H, Tp*-CH3); IR (KBr): v˜ = 2521, 2564 cm 1 (B H); elemental analysis calcd for C30H44N12B2Se2U1: C 36.39, H 4.48, N 16.97; found: C 36.57, H 4.62, N 16.96

Acknowledgements We thank the National Science Foundation (CAREER grant to S.C.B. (No. 1149875)) and Purdue University for financial support. The Labora-

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tory Directed Research and Development program of Lawrence Livermore National Laboratory is acknowledged for support to J.R.W.

Keywords: chalcogens · selenium · sulfur · tridentate ligands · uranium

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Received: August 5, 2013 Published online: October 22, 2013

Chem. Eur. J. 2013, 19, 16176 – 16180

Synthesis of terminal uranium(IV) disulfido and diselenido compounds by activation of elemental sulfur and selenium.

Rare stakes: Terminal uranium(IV) disulfido and diselenido compounds, Tp*2U(E2) (E=S, Se), were synthesized by the activation of elemental chalcogens...
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