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Significant orbital mixing is rare in lanthanide complexes because of the limited radial extent of the 4f orbitals, which results in a generally small stabilization due to 4f orbital interactions. Nevertheless, even a small amount of additional stabilization could enhance lanthanide separations. One lanthanide complex in which orbital mixing has been extensively studied both experimentally and computationally is cerocene, COT2Ce, where COT is cyclooctatetraene. This compound has a singlet ground state with a low-lying, triplet excited state. Previous fluorescence studies on trimethylsilyl-substituted cerocenes indicate the triplet state is 0.4 eV higher in energy than the singlet state. In addition, computational studies predict that the triplet is 0.3 to 1 eV higher in energy than the singlet. The synthesis of highly pure COT2Ce by Walter and Andersen allowed its physical properties to be accurately measured. Using these measurements, we evaluate the stabilization of the 4f orbitals using two, independent approaches. A Hubbard model is used to evaluate the stabilization of the ground state due to orbital mixing. This stabilization, which is also the singlet-triplet gap, is -0.29 eV using this model. This gap was also from the temperature independent paramagnetism of COT2Ce, which yielded a value of -0.32 eV.

Significant orbital mixing is rare in lanthanide complexes because of the limited radial extent of the 4f orbitals, which results in a generally small stabilization due to 4f orbital interactions. Nevertheless, even a small amount of additional stabilization could enhance lanthanide separations. One lanthanide complex in which orbital mixing has been extensively studied both experimentally and computationally is cerocene, COT2Ce, where COT is cyclooctatetraene. This compound has a singlet ground state with a low-lying, triplet excited state. Previous fluorescence studies on trimethylsilyl-substituted cerocenes indicate the triplet state is 0.4 eV higher in energy than the singlet state. In addition, computational studies predict that the triplet is 0.3 to 1 eV higher in energy than the singlet. The synthesis of highly pure COT2Ce by Walter and Andersen allowed its physical properties to be accurately measured. Using these measurements, we evaluate the stabilization of the 4f orbitals using two, independent approaches. A Hubbard model is used to evaluate the stabilization of the ground state due to orbital mixing. This stabilization, which is also the singlet-triplet gap, is -0.29 eV using this model. This gap was also from the temperature independent paramagnetism of COT2Ce, which yielded a value of -0.32 eV.

A general synthetic procedure to neutral homo- and heterobimetallic cage compounds exhibiting various structural motifs of the polypnictogen ligands starting from [Cp*Fe(η5-E5)] (E = P (1), As (2); Cp* = C5Me5) is reported. The impact of the implemented transition metal precursors {Cp′′′M} (M = Cr, Mn, Fe, Ni; Cp′′′ = 1,2,4-tBu3C5H2) emphasises the variability of the isolated complexes exhibiting a broad variety of structural motifs of the pnictogen ligands. Spectroscopic, crystallographic, and theoretical investigations provide insight into the structure of the partially unprecedented polypnictogen ligands. [ABSTRACT FROM AUTHOR]

Characterization of paramagnetic compounds, in particular regarding the detailed conformation and electronic structure, remains a challenge, and -- still today it often relies solely on the use of X-ray crystallography, thus limiting the access to electronic structure information. This is particularly true for lanthanide elements that are often associated with peculiar structural and electronic features in relation to their partially filled f-shell. Here, we develop a methodology based on the combined use of state-of-theart magnetic resonance spectroscopies (EPR and solid-state NMR) and computational approaches as well as magnetic susceptibility measurements to determine the electronic structure and geometry of a paramagnetic Yb(III) alkyl complex, Yb(III)[CH(SiMe3)2]3, a prototypical example, which contains notable structural features according to X-ray crystallography. Each of these techniques revealed specific information about the geometry and electronic structure of the complex. Taken together, both EPR and NMR, augmented by quantum chemical calculations, provide a detailed and complementary understanding of such paramagnetic compounds. In particular, the EPR and NMR signatures point to the presence of three-centre--two-electron Yb-γ-Me-β-Si secondary metal--ligand interactions in this otherwise tri-coordinate metal complex, similarly to its diamagnetic Lu analogues. The electronic structure of Yb(III) can be described as a single 4f13 configuration, while an unusually large crystal-field splitting results in a thermally isolated ground Kramers doublet. Furthermore, the computational data indicate that the Yb--carbon bond contains some p-character, reminiscent of the so-called a-H agostic interaction. [ABSTRACT FROM AUTHOR]

New synthetic procedures for the preparation of Ce(cot)2, cerocene, from [Li(thf)4][Ce(cot)2], and Ce2(cot)3 in high yield and purity are reported. Heating solid Ce(cot)2 yields Ce2(cot)3 and COT while heating Ce2(cot)3 with an excess of COT in C6D6 to 65oC over four months yields Ce(cot)2. The solid state magnetic susceptibility of these three organocerium compounds shows that Ce(cot)2 behaves as a TIP (temperature independent paramagnet) over the temperature range of 5-300 K, while that of Ce2(cot)3 shows that the spin carriers are antiferromagnetically coupled below 10 K; above 10 K, the individual spins are uncorrelated, and [Ce(cot)2]- behaves as an isolated f1 paramagnet. The EPR at 1.5K for Ce2(cot)3 and [Ce(cot)2]- have ground state of MJ= +- 1/2. The LIII edge XANES of Ce(cot)2 (Booth, C.H.; Walter, M.D.; Daniel, M.; Lukens, W.W., Andersen, R.A., Phys. Rev. Lett. 2005, 95, 267202) and 2Ce2(cot)3 over 30-500 K are reported; the Ce(cot)2 XANES spectra show Ce(III) and Ce(IV) signatures up to a temperature of approximately 500 K, whereupon the Ce(IV) signature disappears, consistent with the thermal behavior observed in the melting experiment. The EXAFS of Ce(cot)2 and Ce2(cot)3 are reported at 30 K; the agreement between the molecular parameters for Ce(cot)2 derived from EXAFS and single crystal X-ray diffraction data are excellent. In the case of Ce2(cot)3 no X-ray diffraction data are known to exist, but the EXAFS are consistent with a "triple-decker" sandwich structure. A molecular rationalization is presented for the electronic structure of cerocene having a multiconfiguration ground state that is an admixture of the two configurations Ce(III, 4f1)(cot1.5-)2 and Ce(IV, 4f0)(cot2-)2; the multiconfigurational ground state has profound effects on the magnetic properties and on the nature of the chemical bond in cerocene and, perhaps, other molecules.

The complexes [Ce(tmtaa)2], [Ce(tmtaa)(tmtaaH)] and [Ce2(tmtaa)3(thf)2] are obtained from Ce[N(SiMe3)2]3 and tmtaaH2, the macrocyclic ligand 6,8,15,17-tetramethyldibenzotetraaza[14]-annulene, depending on the stoichiometry, solvent and temperature. The crystal structure of Ce(tmtaa)2 is isostructural with Zr(tmtaa)2, however magnetic susceptibility measurements in the range 5-300 K show that Ce(tmtaa)2 is not diamagnetic, but is a temperature-independent paramagnet (TIP), similar to Ce(cot)2, cerocene.

The paramagnetic 1:1 coordination complexes of (C5Me5)2Yb with a series of 4,4'-disubstituted bipyridines, bipy-X, where X is Me, tert-Bu, OMe, Ph, CO2Me, and CO2Et have been prepared. All of the complexes are paramagnetic and the values of the magnetic susceptibility as a function of temperature show that these values are less than expected for the cation, [(C5Me5)2Yb(III)(bipy-X)]+, which have been isolated as the cation-anion ion-pairs [(C5Me5)2Yb(III)(bipy-X)]+[(C5Me5)2YbI2]f fnfn where X is CO2Et, OMe and Me. The 1H NMR chemical shifts (293 K) for the methine resonances located at the 6,6' site in the bipy-X ring show a linear relationship with the values of chiT (300 K) for the neutral complexes which illustrates that the molecular behavior does not depend upon the phase with one exception, viz., (C5Me5)2Yb(bipy-Me). Single crystals of the 4,4'-dimethylbipyridine complex undergo an irreversible, abrupt first order phase change at 228 K that shatters the single crystals. The magnetic susceptibility, represented in a delta vs. T plot, on this complex, in polycrystalline form undergoes reversible abrupt changes in the temperature regime 205 - 212 K, which is suggested to be due to the way the individual molec ular units pack in the unit cell. A qualitative model is proposed that accounts for the sub-normal magnetic moments in these ytterbocene-bipyridine complexes.

Reduction of the uranium metallocene, [eta5-1,2,4-(Me3C)3C5H2]2UCl2 (1), Cp'2UCl2, in the presence of 2,2'-bipyridyl and sodium naphthalene gives the dark green metallocene complex, Cp'2U(bipy) (6), which reacts with p-tolylazide or pyridine-N-oxide to give Cp'2U=N(p-tolyl) (7) or Cp'2U(O)(py) (8), respectively. The Lewis acid, BPh3, precipitates Ph3B(py) and gives the base-free oxo, Cp'2UO (10), which crystallizes from pentane. The oxometallocene 10 behaves as a nucleophile with Me3SiX reagents but it does not exhibit cycloaddition behavior with acetylenes, suggesting that the polar resonance structure, Cp'2U+-O- dominates the double bond resonance structure Cp'2U=O.

The Lewis base-supported uranium terminal imido metallocene [η5-1,2,4-(Me3Si)3C5H2]2UvN(p-tolyl) (dmap) (1) readily reacts with various small molecules such as internal alkynes, isothiocyanates, thioketones, amidates, organic nitriles and imines, chlorosilanes, copper iodide, diphenyl disulfide, organic azides and diazoalkane derivatives. For example, treatment of 1 with PhCuCCuCPh and PhNCS forms metallaheterocycles originating from a [2 + 2] cycloaddition to yield [η5-1-(p-tolyl)NC(Ph)vCHCvC(Ph) CH2Si(Me)2-2,4-(Me3Si)2C5H2][η5-1,2,4-(Me3Si)3C5H2]U (2) and [η5-1,2,4-(Me3Si)3C5H2]2U[N(p-tolyl)C (vNPh)S](dmap) (3), respectively. The reaction of 1 with the thioketone Ph2CS forms the known uranium sulfido complex [η5-1,2,4-(Me3Si)3C5H2]2US(dmap) (4), which reacts with a second molecule of Ph2CS to give the disulfido compound [η5-1,2,4-(Me3Si)3C5H2]2U(S2CPh2) (5). The imido moiety also promotes deprotonation reactions as illustrated in the reactions with the amide PhCONH(p-tolyl), the nitrile PhCH2CN and the imine (p-tolyl)2CvNH to form the bis-amidate [η5-1,2,4-(Me3Si)3C5H2]2U[OC(Ph)N(ptolyl)] 2 (7), and the iminato complexes [η5-1,2,4-(Me3Si)3C5H2]2U[N(p-tolyl)C(CH2Ph)vNH](NvCvCHPh) (8) and [η5-1,2,4-(Me3Si)3C5H2]2U[NH(p-tolyl)][NvC(p-tolyl)2] (9), respectively. Addition of PhSiH2Cl to 1 yields [η5-1,2,4-(Me3Si)3C5H2]2U(Cl)[N(p-tolyl)SiH2Ph] (10). In contrast, the uranium(V) imido complexes [η5-1,2,4-(Me3Si)3C5H2]2UvN(p-tolyl)(I) (11) and [η5-1,2,4-(Me3Si)3C5H2]2UvN(p-tolyl)(SPh) (12), may be isolated upon addition of CuI or Ph2S2 to 1, respectively. Uranium(VI) bis-imido metallocenes [η5-1,2,4-(Me3Si)3C5H2]2UvN(p-tolyl)(vNR) (R = p-tolyl (13), mesityl (14)) and [η5-1,2,4-(Me3Si)3C5H2]2UvN(ptolyl)[ vNNv(9-C13H8)] (15) are accessible from 1 on exposure to RN3 (R = p-tolyl, mesityl) and 9-diazofluorene, respectively. Complexes 2, 3, 5, and 7-15 were characterized by various spectroscopic techniques and, in addition, compounds 2, 3, 5, and 7-13 were structurally authenticated by single-crystal X-ray diffraction analyses. [ABSTRACT FROM AUTHOR]