Investigating Steric and Electronic Effects in the Synthesis of Square Planar 6d1 Th(III) Complexes.

The factors affecting the formation and crystal structures of unusual 6d1 Th(III) square planar aryloxide complexes, as exemplified by [Th(OArMe)4]1- (OArMe = OC6H2tBu2-2,6-Me-4), were explored by synthetic and reduction studies of a series of related Th(IV) tetrakis(aryloxide) complexes, Th(OArR)4 (OArR = OC6H2tBu2-2,6-R-4). Specifically, electronic, steric, and countercation effects were explored by varying the aryloxide ligand, the alkali metal reducing agent, and the alkali metal chelating agent. Salt metathesis reactions between ThBr4(DME)2 (DME = 1,2-dimethoxyethane) and 4 equiv of the appropriate potassium aryloxide salt were used to prepare a series of Th(IV) aryloxide complexes in high yields: Th(OArH)4 (OArH = OC6H3tBu2-2,6), Th(OArtBu)4 (OArtBu = OC6H2tBu3-2,4,6), Th(OArOMe)4 (OArOMe = OC6H2tBu2-2,6-OMe-4), and Th(OArPh)4 (OArPh = OC6H2tBu2-2,6-Ph-4). Th(OArH)4 can be reduced by KC8, Na, or Li in the absence or presence of 2.2.2-cryptand (crypt) or 18-crown-6 (crown) to form dark purple solutions that have EPR and UV-visible spectra similar to those of the square planar Th(III) complex, [Th(OArMe)4]1-. Hence, the para position of the aryloxide ligand does not have to be alkylated to obtain the Th(III) complexes. Furthermore, reduction of Th(OArOMe)4, Th(OArtBu)4, and Th(OArPh)4 with KC8 in THF generated purple solutions with EPR and UV-visible spectra that are similar to those of the previously reported Th(III) anion, [Th(OArMe)4]1-. Although many of these reduction reactions did not produce single crystals suitable for study by X-ray diffraction, reduction of Th(OArH)4, Th(OArtBu)4, and Th(OArOMe)4 with Li provided X-ray quality crystals whose structures had square planar coordination geometries. Reduction of Th(OArPh)4 with Li also gave a product with EPR and UV-visible spectra that matched those of [Th(OArMe)4]1-, but X-ray quality crystals of the reduction product were too unstable to provide data. Neither Th(Odipp)4(THF)2 (Odipp = OC6H3iPr2-2,6) nor Th(Odmp)4(THF)2 (Odmp = OC6H3Me2-2,6) could be reduced to Th(III) products under similar conditions. Reduction of U(OArH)3(THF) with KC8 in the presence of 2.2.2-cryptand (crypt) was examined for comparison and formed [K(crypt)][U(OArH)4], which has a tetrahedral arrangement of the aryloxide ligands. Moreover, no further reduction was observed when either [K(crypt)][U(OArH)4] or [K(crown)(THF)2][U(OArH)4] were treated with KC8 or Li.

Perplexing EPR Signals from 5f36d1 U(II) Complexes.

Metal complexes with unpaired electrons in orbitals of different angular momentum quantum numbers (e.g., f and d orbitals) are unusual and opportunities to study the interactions among these electrons are rare. X-band electron paramagnetic resonance (EPR) data were collected at <10 and 77 K on 10 U(II) complexes with 5f36d1 electron configurations and on some analogous Ce(II), Pr(II), and Nd(II) complexes with 4fn5d1 electron configurations. The U(II) compounds unexpectedly display similar two-line axial signals with g|| = 2.04 and g⊥ = 2.00 at 77 K. In contrast, U(II) complexes with 5f4 configurations are EPR-silent. Unlike U(II), the congenic 4f35d1 Nd(II) complex is EPR-silent. The Ce(II) complex with a 4f15d1 configuration is also EPR-silent, but a signal is observed for the Pr(II) complex, which has a 4f25d1 configuration. Whether or not an EPR signal is expected for these complexes depends on the coupling between f and d electrons. Since the coupling in U(II) systems is expected to be sufficiently strong to preclude an EPR signal from compounds with a 5f36d1 configuration, the results are viewed as unexplained phenomena. However, they do show that 5f36d1 U(II) samples can be differentiated from 5f4 U(II) complexes by EPR spectroscopy.

Synthesis and Crystallographic Characterization of a Reduced Bimetallic Yttrium ansa-Metallocene Hydride Complex, [K(crypt)][(µ-CpAn)Y(µ-H)]2 (CpAn = Me2Si[C5H3(SiMe3)-3]2), with a 3.4 Å Yttrium-Yttrium Distance.

The reduction of a bimetallic yttrium ansa-metallocene hydride was examined to explore the possible formation of Y-Y bonds with 4d1 Y(II) ions. The precursor [CpAnY(µ-H)(THF)]2 (CpAn = Me2Si[C5H3(SiMe3)-3]2) was synthesized by hydrogenolysis of the allyl complex CpAnY(η3-C3H5)(THF), which was prepared from (C3H5)MgCl and [CpAnY(µ-Cl)]2. Treatment of [CpAnY(µ-H)(THF)]2 with excess KC8 in the presence of one equivalent of 2.2.2-cryptand (crypt) generates an intensely colored red-brown product crystallographically identified as [K(crypt)][(µ-CpAn)Y(µ-H)]2. The two rings of each CpAn ligand in the reduced anion [(µ-CpAn)Y(µ-H)]21- are attached to two yttrium centers in a "flyover" configuration. The 3.3992(6) and 3.4022(7) Å Y···Y distances between the equivalent metal centers within two crystallographically independent complexes are the shortest Y···Y distances observed to date. Ultraviolet-visible (UV-visible)/near infrared (IR) and electron paramagnetic resonance (EPR) spectroscopy support the presence of Y(II), and theoretical analysis describes the singly occupied molecular orbital (SOMO) as an Y-Y bonding orbital composed of metal 4d orbitals mixed with metallocene ligand orbitals. A dysprosium analogue, [K(18-crown-6)(THF)2][(µ-CpAn)Dy(µ-H)]2, was also synthesized, crystallographically characterized, and studied by variable temperature magnetic susceptibility. The magnetic data are best modeled with the presence of one 4f9 Dy(III) center and one 4f9(5dz2)1 Dy(II) center with no coupling between them. CASSCF calculations are consistent with magnetic measurements supporting the absence of coupling between the Dy centers.

Trimethyltriazacyclohexane coordination chemistry of simple rare-earth metal salts.

Reactions of 1,3,5-trimethyl-triazacyclohexane (Me3tach) with common rare-earth metal iodide, chloride, and triflate salts were examined to determine the capacity of this inexpensive chelate to provide alternative precursors for THF-free reactions. The reaction of LaI3(THF)4 and CeI3(THF)4 with 1,3,5-trimethyl-triazacyclohexane in THF generated toluene soluble (Me3tach)2LnI3, 1-Ln, in which the Ln center has a tri-capped trigonal prismatic geometry with two eclipsed Me3tach rings. Reaction with NdI3(THF)3.5 forms the analogous 1-Nd, but a different structure with one outer sphere iodide, [(Me3tach)2NdI2][I], 2-Nd, is also accessible and has a structure reminiscent of bent metallocenes. The reaction of LaCl3 and Me3tach forms the less soluble (Me3tach)2LaCl3, which has a structure analogous to 1-Ln with eclipsed Me3tach rings. The mono-ring yttrium complex, (Me3tach)YCl3(THF)2, could be isolated from the reaction of YCl3 with Me3tach. Reactions of La(OTf)3 with Me3tach were sensitive to the presence of residual proton sources as exemplified by the isolation of {[(Me3tach)La(µ-OH)(µ-OTf)]2(µ-OTf)2}2, 5-La, and [HMe3tach][(Me3tach)2La-(OTf)4], 6-La. SmI2 reacts with Me3tach to produce the Sm(II) complex, (Me3tach)2SmI2(THF), 7-Sm, but 2-Sm can also form in this reaction. Complexes of the larger 1,4,7-trimethyltriazacyclononane (Me3tacn) ligand, namely (Me3tacn)LaI3(THF), (Me3tacn)YCl3, and (Me3tacn)SmI2(THF) were synthesized for comparison. Several examples of the protonated ligands with simple counteranions, [HMe3tach][X] (X = Cl, Br, I) and [HMe3tacn][OTf], were identified in the course of these studies.

Synthesis of Trimethyltriazacyclohexane (Me3tach) Sandwich Complexes of Uranium, Neptunium, and Plutonium Triiodides: (Me3tach)2AnI3.

1,3,5-Trimethyl-1,3,5-triazacyclohexane (Me3tach) readily complexes uranium triiodide to form (Me3tach)2UI3. The complex is soluble in THF and arenes and can function as a source of UI3 to form organometallic U(III) complexes. When dissolved in pyridine (py), (Me3tach)2UI3 forms (Me3tach)UI3(py)2. A related complex with the larger 1,4,7-trimethyl-1,4,7-triazacyclononane (Me3tacn) ligand, namely (Me3tacn)UI3(THF), was synthesized for comparison. Since X-ray quality crystals of (Me3tach)2UI3 can be synthesized in high yield even with small-scale reactions, the system is ideal for extension to transuranium elements. Accordingly, the neptunium and plutonium complexes (Me3tach)2NpI3 and (Me3tach)2PuI3 were synthesized in an analogous manner from NpI3(THF)4 and PuI3(THF)4, respectively.

Reduction of Rare-Earth Metal Complexes Induced by γ Irradiation.

The utility of γ irradiation for generating unstable, low oxidation state molecular species containing rare-earth metal ions in frozen solution has been examined. The method was evaluated by irradiating Ln(III) precursors (Ln = Sc, Y, and La) in a solid matrix of 2-methyltetrahydrofuran at 77 K with a 700 keV 137Cs source to generate free electrons capable of reducing the Ln(III) species. These experiments yielded EPR and UV-visible spectroscopic data that matched those of the known Ln(II) species [(C5H4SiMe3)3YII]1-, [(C5H4SiMe3)3LaII]1-, and {ScII[N(SiMe3)2]3}1-. Irradiation of the La(III) complex LaIII[N(SiMe3)2]3 by this method gave EPR and UV-visible absorption spectra consistent with {LaII[N(SiMe3)2]3}1-, a species that had previously eluded preparation by chemical reduction. Specifically, the irradiation product exhibited an axial EPR spectrum split into eight lines by the I = 7/2 139La nucleus (g⊥ = 1.98, g|| = 2.06, Aave = 519.1 G). The UV-visible absorption spectrum contains broad bands centered at 390 and 670 nm that are consistent with a La(II) ion in a trigonal ligand environment based on time-dependent density functional theory which qualitatively reproduces the observed spectrum. Additionally, the rate of formation of the [(C5H4SiMe3)3YII]1- species during the irradiation of (C5H4SiMe3)3YIII was monitored by measuring the concentration via UV-visible spectroscopy over time to provide data on the rate at which a molecular species is reduced in a glass via γ irradiation.

Identification of the U(V) complex (C5Me5)2UVI(NSiMe3) in the reaction of (C5Me5)2UIIII(THF) with N3SiMe3.

The U(V) imido complex (C5Me5)2UVI(NSiMe3), 1, was crystallographically characterized from the reaction of (C5Me5)2UIIII(THF) with N3SiMe3 which demonstrates that it can be an intermediate in the reaction which ultimately forms (C5Me5)2UVI(NSiMe3)2 and (C5Me5)2UIVI2. U(V) intermediates have been proposed in such reactions, but have not been previously observed. The direct observation of 1 provides insight into the reaction mechanisms of U(III) compounds with azide reagents.

Expanding Bismuth Trihalide Coordination Chemistry with Trimethyltriazacyclohexane and Trimethyltriazacyclononane.

1,3,5-Trimethyltriazacyclohexane, Me3tach, readily adds to bismuth triiodide to form a variety of new coordination compounds depending on the stoichiometry, solvent, and crystallization conditions. X-ray crystallographic evidence has been obtained for both 2:1 and 1:1 Me3tach:Bi complexes with formulas of [(Me3tach)2BiI2][(Me3tach)BiI4], [(Me3tach)2BiI2]3[Bi2I9][I][HMe3tach]·THF, and (Me3tach)BiI3(py)2. The related chloride structure (Me3tach)BiCl3(py)2 forms from BiCl3. The structure of (Me3tacn)BiI3 with the larger chelate, 1,4,7-trimethyltriazacyclononane, Me3tacn, was obtained for comparison, and the polymeric structure of BiI3 in THF was defined as [BiI(THF)(µ-I)2]n.

Synthesis and Reduction of Heteroleptic Bis(cyclopentadienyl) Uranium(III) Complexes.

Heteroleptic U(III) complexes supported by bis(cyclopentadienyl) frameworks have been synthesized to examine their suitability as precursors to U(II) complexes. The newly synthesized (C5Me5)2U(OC6H2tBu2-2,6-Me-4), (C5Me5)2U(OC6H2Ad2-2,6-tBu-4) (Ad = 1-adamantyl), (C5Me5)2U(C5H5), and (C5Me5)2U(C5Me4H) are compared with (C5Me5)2U[N(SiMe3)2], (C5Me5)2U[CH(SiMe3)2], and (C5Me5)U[N(SiMe3)2]2. An improved synthesis of (C5Me5)2U(µ-Ph)2BPh2 was developed, which was used to synthesize (C5Me5)2U(C5Me4H). Since the X-ray crystal structure of (C5Me5)2U(OC6H2tBu2-2,6-Me-4) contained two very different molecules in the asymmetric unit with 115.7(5)° and 166.0(5)° U-O-Cipso angles, the (C5Me4H)2U(OC6H2tBu2-2,6-Me-4) and (C5Me5)2Ce(OC6H2tBu2-2,6-Me-4) analogues were synthesized and characterized by X-ray diffraction for comparison. Electrochemical studies in THF with a 100 mM [nBu4N][BPh4] supporting electrolyte showed U(IV)/U(III) and U(III)/U(II) redox couples for all the heteroleptic complexes except (C5Me5)2U(C5H5). Chemical reduction of all heteroleptic compounds formed dark blue solutions characteristic of U(II) when reacted with KC8 at -78 °C, but none formed isolable U(II) complexes. The targeted U(II) complexes, [(C5Me5)2U(OC6H2tBu2-2,6-Me-4)]1-, {(C5Me5)2U[CH(SiMe3)2]}1-, [(C5Me5)2U(C5H5)]1-, and [(C5Me5)2U(C5Me4H)]1-, were analyzed by density functional theory, and a 5f36d1 electron configuration was found to be the ground state in each case.

Anion-induced disproportionation of Th(III) complexes to form Th(II) and Th(IV) products.

A new synthesis of Th(II) complexes has been identified involving addition of simple MX salts (M = Li, Na, K; X = H, Cl, Me, N3) to Cp''3ThIII [Cp'' = [C5H3(SiMe3)2] in the presence of 18-crown-6 or 2.2.2-cryptand, forming [M(chelate)][Cp''3ThII] and Cp''3ThIVX. Cptet3ThIII (Cptet = C5Me4H) reacts with KH to form Cptet3ThIVH and the C-H bond activation product, [K(crypt)]{[Cptet2ThIVH[η1:η5-C5Me3H(CH2)]}.

Isolation and characterization of a californium metallocene.

Californium (Cf) is currently the heaviest element accessible above microgram quantities. Cf isotopes impose severe experimental challenges due to their scarcity and radiological hazards. Consequently, chemical secrets ranging from the accessibility of 5f/6d valence orbitals to engage in bonding, the role of spin-orbit coupling in electronic structure, and reactivity patterns compared to other f elements, remain locked. Organometallic molecules were foundational in elucidating periodicity and bonding trends across the periodic table1-3, with a twenty-first-century renaissance of organometallic thorium (Th) through plutonium (Pu) chemistry4-12, and to a smaller extent americium (Am)13, transforming chemical understanding. Yet, analogous curium (Cm) to Cf chemistry has lain dormant since the 1970s. Here, we revive air-/moisture-sensitive Cf chemistry through the synthesis and characterization of [Cf(C5Me4H)2Cl2K(OEt2)]n from two milligrams of 249Cf. This bent metallocene motif, not previously structurally authenticated beyond uranium (U)14,15, contains the first crystallographically characterized Cf-C bond. Analysis suggests the Cf-C bond is largely ionic with a small covalent contribution. Lowered Cf 5f orbital energy versus dysprosium (Dy) 4f in the colourless, isoelectronic and isostructural [Dy(C5Me4H)2Cl2K(OEt2)]n results in an orange Cf compound, contrasting with the light-green colour typically associated with Cf compounds16-22.

A Rare-Earth Metal Retrospective to Stimulate All Fields.

Formulating insightful questions and experiments is crucial to the advancement of science. The purpose of this Perspective is to encourage scientists in all areas of chemistry to ask more "What if?" questions: What if we tried this experiment? What if we used these conditions? What if that idea is not correct? To stimulate this thinking, a retrospective analysis of a specific field, in this case rare-earth metal chemistry, is presented that describes the "What if?" questions that could have and should have been asked earlier based on our current knowledge. The goal is to provide scientists with a historical perspective of discovery that exemplifies how previous views in chemistry were often narrowed by predominant beliefs in principles that were incorrect. The same situation is likely to exist today, but we do not realize the limitations! Hopefully, this analysis can be used as a springboard for posing important "What if?" questions that should be asked right now in every area of chemical research.

Density Functional Theory Analysis of the Importance of Coordination Geometry for 5f36d1 versus 5f4 Electron Configurations in U(II) Complexes.

Density functional theory (DFT) calculations on four known and seven hypothetical U(II) complexes indicate the importance of coordination geometry in favoring 5f36d1 versus 5f4 electronic ground states. The known [Cp″3U]-, [Cptet3U]-, and [U(NR2)3]- [Cp″ = C5H3(SiMe3)2, Cptet = C5Me4H, and R = SiMe3] anions were found to have 5f36d1 ground states, while a 5f4 ground state was found for the known compound (NHAriPr6)2U. The UV-visible spectra of the known 5f36d1 compounds were simulated via time-dependent DFT and are in qualitative agreement with the experimental spectra. For the hypothetical U(II) compounds, the 5f36d1 configuration is predicted for [U(CHR2)3]-, [U(H3BH)3]-, [U(OAr')4]2-, and [(C8H8)U]2- (OAr' = O-C6H2tBu2-2,6-Me-4). In the case of [U(bnz')4]2- (bnz' = CH2-C6H4tBu-4), a 5f3 configuration with a ligand-based radical was found as the ground state.

Evaluating electrochemical accessibility of 4fn5d1 and 4fn+1 Ln(II) ions in (C5H4SiMe3)3Ln and (C5Me4H)3Ln complexes.

The reduction potentials (reported vs. Fc+/Fc) for a series of Cp'3Ln complexes (Cp' = C5H4SiMe3, Ln = lanthanide) were determined via electrochemistry in THF with [nBu4N][BPh4] as the supporting electrolyte. The Ln(III)/Ln(II) reduction potentials for Ln = Eu, Yb, Sm, and Tm (-1.07 to -2.83 V) follow the expected trend for stability of 4f7, 4f14, 4f6, and 4f13 Ln(II) ions, respectively. The reduction potentials for Ln = Pr, Nd, Gd, Tb, Dy, Ho, Er, and Lu, that form 4fn5d1 Ln(II) ions (n = 2-14), fall in a narrow range of -2.95 V to -3.14 V. Only cathodic events were observed for La and Ce at -3.36 V and -3.43 V, respectively. The reduction potentials of the Ln(II) compounds [K(2.2.2-cryptand)][Cp'3Ln] (Ln = Pr, Sm, Eu) match those of the Cp'3Ln complexes. The reduction potentials of nine (C5Me4H)3Ln complexes were also studied and found to be 0.05-0.24 V more negative than those of the Cp'3Ln compounds.

Electrochemical studies of tris(cyclopentadienyl)thorium and uranium complexes in the +2, +3, and +4 oxidation states.

Electrochemical measurements on tris(cyclopentadienyl)thorium and uranium compounds in the +2, +3, and +4 oxidation states are reported with C5H3(SiMe3)2, C5H4SiMe3, and C5Me4H ligands. The reduction potentials for both U and Th complexes trend with the electron donating abilities of the cyclopentadienyl ligand. Thorium complexes have more negative An(iii)/An(ii) reduction potentials than the uranium analogs. Electrochemical measurements of isolated Th(ii) complexes indicated that the Th(iii)/Th(ii) couple was surprisingly similar to the Th(iv)/Th(iii) couple in Cp''-ligated complexes. This suggested that Th(ii) complexes could be prepared from Th(iv) precursors and this was demonstrated synthetically by isolation of directly from UV-visible spectroelectrochemical measurements and reactions of with elemental barium indicated that the thorium system undergoes sequential one electron transformations.

In search of tris(trimethylsilylcyclopentadienyl) thorium.

Reduction of Cp'3ThCl, Cp'3ThBr, and Cp'3ThI (Cp' = C5H4SiMe3) with potassium graphite generates dark blue solutions with reactivity and spectroscopic properties consistent with the formation of Cp'3Th. The EPR and UV-visible spectra of the solutions are similar to those of crystallographically-characterized tris(cyclopentadienyl) Th(iii) complexes: [C5H3(SiMe3)2]3Th, (C5Me4H)3Th, (C5tBu2H3)3Th, and (C5Me5)3Th. Density functional theory (DFT) analysis indicates that the UV-visible spectrum is consistent with Cp'3Th and not [Cp'3ThBr]1-. Although single crystals of Cp'3Th have not been isolated, the blue solution reacts with Me3SiCl, I2, and HC[triple bond, length as m-dash]CPh to afford products expected from Cp'3Th, namely, Cp'3ThCl, Cp'3ThI, and Cp'3Th(C[triple bond, length as m-dash]CPh), respectively. Reactions with MeI give mixtures of Cp'3ThI and Cp'3ThMe. Evidence for further reduction of the blue solutions to a Cp'-ligated Th(ii) complex has not been observed. The crystal structures of Cp'3ThMe and (Cp'3Th)2(µ-O) were also determined as part of these studies.