4f-Orbital mixing increases the magnetic susceptibility of Cp'3Eu.

Traditional models of lanthanide electronic structure suggest that bonding is predominantly ionic, and that covalent orbital mixing is not an important factor in determining magnetic properties. Here, 4f orbital mixing and its impact on the magnetic susceptibility of Cp'3Eu (Cp' = C5H4SiMe3) was analyzed experimentally using magnetometry and X-ray absorption spectroscopy (XAS) methods at the C K-, Eu M5,4-, and L3-edges. Pre-edge features in the experimental and TDDFT-calculated C K-edge XAS spectra provided unequivocal evidence of C 2p and Eu 4f orbital mixing in the π-antibonding orbital of a' symmetry. The charge-transfer configurations resulting from 4f orbital mixing were identified spectroscopically by using Eu M5,4-edge and L3-edge XAS. Modeling of variable-temperature magnetic susceptibility data showed excellent agreement with the XAS results and indicated that increased magnetic susceptibility of Cp'3Eu is due to removal of the degeneracy of the 7F1 excited state due to mixing between the ligand and Eu 4f orbitals.

Synthesis and reduction of [(C5H4SiMe3)2Ln(µ-OR)]2 (Ln = La, Ce) complexes: structural effects of bridging alkoxides.

Alcoholysis of Cp'3Ln (Ln = La, Ce; Cp' = C5H4SiMe3) generate high-yielding (72-97%) bimetallic LnIII complexes of [Cp'2Ln(µ-OR)]2 [R = Et, iPr, or C6H4-4-tBu]. Single-crystal X-ray diffraction of these complexes reveal unexpected decreases in Ln⋯Ln distances, increasing Cpcent-Ln-Cpcent angles, and increasing intermolecular C⋯C contacts with bulkier bridging alkoxides, in line with structural control driven by significant dispersion forces. 1H NMR spectroscopy of [Cp'2Ce(µ-OEt)]2 and [Cp'2Ce(µ-OiPr)]2 revealed significantly upfield resonances assigned as methylene and methine moieties of -43.74 and -70.85 ppm, respectively. 2D 1H DOSY NMR experiments of [Cp'2Ce(µ-OiPr)]2 in C6D6 supported a dimeric structure in solution, including in the presence of a Lewis base (i.e., THF). Reduction of [Cp'2La(µ-OiPr)]2 using KC8 in the presence of 2.2.2-cryptand at -78 °C generated a purple solution and X-band EPR spectroscopy revealed an eight-line hyperfine pattern indicative of a LaII species.

Ligand Effects on the Spin Relaxation Dynamics and Coherent Manipulation of Organometallic La(II) Potential Qudits.

We present pulsed electron paramagnetic resonance (EPR) studies on three La(II) complexes, [K(2.2.2-cryptand)][La(Cp')3] (1), [K(2.2.2-cryptand)][La(Cp″)3] (2), and [K(2.2.2-cryptand)][La(Cptt)3] (3), which feature cyclopentadienyl derivatives as ligands [Cp' = C5H4SiMe3; Cp″ = C5H3(SiMe3)2; Cptt = C5H3(CMe3)2] and display a C3 symmetry. Long spin-lattice relaxation (T1) and phase memory (Tm) times are observed for all three compounds, but with significant variation in T1 among 1-3, with 3 being the slowest relaxing due to higher s-character of the SOMO. The dephasing times can be extended by more than an order of magnitude via dynamical decoupling experiments using a Carr-Purcell-Meiboom-Gill (CPMG) sequence, reaching 161 µs (5 K) for 3. Coherent spin manipulation is performed by the observation of Rabi quantum oscillations up to 80 K in this nuclear spin-rich environment (1H, 13C, and 29Si). The high nuclear spin of 139La (I = 7/2), and the ability to coherently manipulate all eight hyperfine transitions, makes these molecules promising candidates for application as qudits (multilevel quantum systems featuring d quantum states; d >2) for performing quantum operations within a single molecule. Application of HYSCORE techniques allows us to quantify the electron spin density at ligand nuclei and interrogate the role of functional groups to the electron spin relaxation properties.

Mechanistic study of pyrazole synthesis via oxidation-induced N-N coupling of diazatitanacycles.

Metal-mediated inner-sphere N-N coupling is an uncommon route to N-N bond formation. Herein, we report a mechanistic study of pyrazole formation via oxidation-induced N-N coupling of diazatitanacycles. In TEMPO oxidation reactions, the first of two oxidations is rate limiting and TEMPO coordination to Ti is critical for reactivity. In oxidations with Fc+ salts, coordinating counteranions such (eg. Cl-) aid an "inner-sphere-like" oxidation.

Reassessment of N2 activation by low-valent Ti-amide complexes: a remarkable side-on bridged bis-N2 adduct is actually an arene adduct.

The complex {(TMEDA)2Li}{[Ti(N(TMS)2)2]2(µ-η2:η2-N2)2} (5-Li) is the only transition metal N2 complex ever reported with two side-on N2 adducts. In this report, the similarity of 5-Li to a new inverse sandwich toluene adduct {(PhMe)K}{[Ti(N(TMS)2)2]2(µ-PhMe)} (6-K) necessitated a re-examination of the structure of 5-Li. Through a reassessment of the original disordered crystal data of 5-Li and new independent syntheses brought about through revisitation of the original reaction conditions, 5-Li has been re-assigned as an inverse sandwich toluene adduct, {(TMEDA)2Li}{[Ti(N(TMS)2)2]2(µ-PhMe)} (6-Li). The original crystal data could be fitted almost equally well to structural solutions as either 5-Li or 6-Li, and this study highlights the importance of a holistic examination of modeled data and the need for secondary/complementary analytical methods in paramagnetic inorganic syntheses, especially when presenting unique and unexpected results. In addition, further examination of reduction reactions of Ti[N(TMS)2]3 and [(TMS)2N]2TiCl(THF) in the presence of KC8 revealed rich solvent- and counterion-dependent chemistry, including several degrees of N2 activation (bridging nitride complexes, terminal bridging N2 complexes) as well as ligand C-H activation.

Electronic Structure Analysis and Reactivity of the Bimetallic Bis-Titanocene Vinylcarboxylate Complex, [(Cp2Ti)2(O2C3TMS2)]†.

Multimetallic redox cooperativity features heavily in both bioinorganic and synthetic reactions. Here, the electronic structure of the bimetallic Ti/Ti complex 11, [(Cp2Ti)2(O2C3TMS2)] has been revisited with EPR, confirming a predominantly TiIII/TiIII electronic structure. Reactions of 11 with 2,6-dimethylphenyl isocyanide (CNXyl), TMSCl, MeI, and BnCl were explored, revealing differential redox chemistry of the bimetallic core. In reactions with CNXyl and TMSCl, the metallacyclic TiIII center remained unperturbed, with reactions taking place at the pendent κ2(O,O)-titanocene fragment, while reaction with MeI resulted in remote oxidation of the metallacyclic Ti center, indicative of a cooperative redox process. All structures were studied via X-ray diffraction and EPR spectroscopic analysis, and their electronic structures are discussed in the context of the covalent bond classification (CBC) electron counting method.

High-Resolution X-ray Photoelectron Spectroscopy of Organometallic (C5H4SiMe3)3LnIII and [(C5H4SiMe3)3LnII]1- Complexes (Ln = Sm, Eu, Gd, Tb).

The capacity of X-ray photoelectron spectroscopy (XPS) to provide information on the electronic structure of molecular organometallic complexes of Ln(II) ions (Ln = lanthanide) has been examined for the first time. XPS spectra were obtained on the air-sensitive molecular trivalent 4fn Cp'3LnIII complexes (Ln = Sm, Eu, Gd, Tb; Cp' = C5H4SiMe3) and compared to those of the highly reactive divalent complexes, [K(crypt)][Cp'3LnII] (crypt = 2.2.2-cryptand), which have either 4fn+1 (Sm, Eu) or 4fn5d1 electron configurations (Gd, Tb). The Ln 4d, Si 2p, and C 1s regions of the Ln(III) and Ln(II) complexes were identified and compared. The metal 4d peaks of these molecular lanthanide complexes were used diagnostically to compare oxidation states. The valence region of the Gd(III) and Gd(II) complexes was also examined with XPS and density function theory/random phase approximation (DFT/RPA) calculations, and this led to the tentative assignment of a signal from the 5d1 electron consistent with a 4f75d1 electron configuration for Gd(II).

Multicomponent syntheses of 5- and 6-membered aromatic heterocycles using group 4-8 transition metal catalysts.

In this Perspective, we discuss recent syntheses of 5- and 6-membered aromatic heterocycles via multicomponent reactions (MCRs) that are catalyzed by group 4-8 transition metals. These MCRs can be categorized based on the substrate components used to generate the cyclized product, as well as on common mechanistic features between the catalyst systems. These particular groupings are intended to highlight mechanistic and strategic similarities between otherwise disparate transition metals and to encourage future work exploring related systems with otherwise-overlooked elements. Importantly, in many cases these early- to mid-transition metal catalysts have been shown to be as effective for heterocycle syntheses as the later (and more commonly implemented) group 9-11 metals.

Stabilization of U(III) to Oxidation and Hydrolysis by Encapsulation Using 2.2.2-Cryptand.

The electrochemical properties of U(III)-in-crypt (crypt = 2.2.2-cryptand) were examined in dimethylformamide (DMF) and acetonitrile (MeCN) to determine the oxidative stability offered by crypt as a ligand. Cyclic voltammetry revealed a U(III)/U(IV) irreversible oxidation at EPA= -0.49 V (vs Fe(C5H5)2+/0) in DMF and at EPA= -0.31 V (vs Fe(C5H5)2+/0) in MeCN. The electrochemistry of U(III)-in-crypt complexes in the presence of water was also examined. These studies are supported by crystallographically characterized examples of U(III)-in-crypt complexes as DMF, MeCN, and water adducts.

A Single Small-Scale Plutonium Redox Reaction System Yields Three Crystallographically-Characterizable Organoplutonium Complexes.

An approach to obtaining substantial amounts of data from a hazardous starting material that can only be obtained and handled in small quantities is demonstrated by the investigation of a single small-scale reaction of cyclooctatetraene, C8H8, with a solution obtained from the reduction of Cp'3Pu (Cp' = C5H4SiMe3) with potassium graphite. This one reaction coupled with oxidation of a product has provided single-crystal X-ray structural data on three organoplutonium compounds as well as information on redox chemistry thereby demonstrating an efficient route to new reactivity and structural information on this highly radioactive element. The crystal structures were obtained from the reduction of C8H8 by a putative Pu(II) complex, (Cp'3PuII)1-, generated in situ, to form the Pu(III) cyclooctatetraenide complex, [K(crypt)][(C8H8)2PuIII], 1-Pu, and the tetra(cyclopentadienyl) Pu(III) complex, [K(crypt)][Cp'4PuIII], 2-Pu. Oxidation of the sample of 1-Pu with Ag(I) afforded a third organoplutonium complex that has been structurally characterized for the first time, (C8H8)2PuIV, 3-Pu. Complexes 1-Pu and 3-Pu contain Pu sandwiched between parallel (C8H8)2- rings. The (Cp'4PuIII)- anion in 2-Pu features three η5-Cp' rings and one η1-Cp' ring, which is a rare example of a formal Pu-C η1-bond. In addition, this study addresses the challenge of small-scale synthesis imparted by radiological and material availability of transuranium isotopes, in particular that of pure metal samples. A route to an anhydrous Pu(III) starting material from the more readily available PuIVO2 was developed to facilitate reproducible syntheses and allow complete spectroscopic analysis of 1-Pu and 2-Pu. PuIVO2 was converted to PuIIIBr3(DME)2 (DME = CH3OCH2CH2OCH3) and subsequently PuIIIBr3(THF)x, which was used to independently synthesize 1-Pu, 2-Pu, and 3-Pu.

Crystal structure of the [(THF)Cs(µ-η5:η5-Cp')3Yb] n oligomer.

The green compound poly[(tetra-hydro-furan)-tris-[µ-η5:η5-1-(tri-methyl-sil-yl)cyclo-penta-dien-yl]caesium(I)ytterbium(II)], [CsYb(C8H13Si)3(C4H8O)] n or [(THF)Cs(µ-η5:η5-Cp')3YbII] n was synthesized by reduction of a red THF solution of (C5H4SiMe3)3YbIII with excess Cs metal and identified by X-ray diffraction. The compound crystallizes as a two-dimensional array of hexa-gons with alternating CsI and YbII ions at the vertices and cyclo-penta-dienyl groups bridging each edge. This, based off the six-electron cyclo-penta-dienyl rings occupying three coordination positions, gives a formally nine-coordinate tris-(cyclo-penta-dien-yl) coordination environment to Yb and the Cs is ten-coordinate due to the three cyclo-penta-dienyl rings and a coordinated mol-ecule of THF. The complex comprises layers of Cs3Yb3 hexa-gons with THF ligands and Me3Si groups in between the layers. The Yb-C metrical parameters are consistent with a 4f 14 YbII electron configuration.

Synthesis of LnII -in-Cryptand Complexes by Chemical Reduction of LnIII -in-Cryptand Precursors: Isolation of a NdII -in-Cryptand Complex.

Lanthanide triflates have been used to incorporate NdIII and SmIII ions into the 2.2.2-cryptand ligand (crypt) to explore their reductive chemistry. The Ln(OTf)3 complexes (Ln=Nd, Sm; OTf=SO3 CF3 ) react with crypt in THF to form the THF-soluble complexes [LnIII (crypt)(OTf)2 ][OTf] with two triflates bound to the metal encapsulated in the crypt. Reduction of these LnIII -in-crypt complexes using KC8 in THF forms the neutral LnII -in-crypt triflate complexes [LnII (crypt)(OTf)2 ]. DFT calculations on [NdII (crypt)]2+ ], the first NdII cryptand complex, assign a 4f4 electron configuration to this ion.

Facile Encapsulation of Ln(II) Ions into Cryptate Complexes from LnI2(THF)2 Precursors (Ln = Sm, Eu, Yb).

The reactivity of LnI2(THF)2 (Ln = Sm, Eu, Yb; THF = tetrahydrofuran) with 2.2.2-cryptand (crypt) was explored to see if these readily accessible precursors could provide new examples of lanthanide-in-crypt complexes. The crystallographically characterized Ln(II)-in-crypt complexes [Ln(crypt)(DMF)2][I]2 (Ln = Sm, Eu) and [Yb(crypt)(DMF)][I]2 (DMF = dimethylformamide) were synthesized by reacting LnI2(THF)2 (Ln = Sm, Eu, Yb) with crypt in THF and recrystallizing from DMF. Crystallographic data were also obtained on the Ln(II)-in-crypt (Ln = Sm, Eu) complexes [Ln(crypt)(DMF)2][BPh4]2, which were synthesized by addition of 2 equiv of NaBPh4 to [Ln(crypt)(DMF)2][I]2.

Engineering electronic structure to prolong relaxation times in molecular qubits by minimising orbital angular momentum.

The proposal that paramagnetic transition metal complexes could be used as qubits for quantum information processing (QIP) requires that the molecules retain the spin information for a sufficient length of time to allow computation and error correction. Therefore, understanding how the electron spin-lattice relaxation time (T1) and phase memory time (Tm) relate to structure is important. Previous studies have focused on the ligand shell surrounding the paramagnetic centre, seeking to increase rigidity or remove elements with nuclear spins or both. Here we have studied a family of early 3d or 4f metals in the +2 oxidation states where the ground state is effectively a 2S state. This leads to a highly isotropic spin and hence makes the putative qubit insensitive to its environment. We have studied how this influences T1 and Tm and show unusually long relaxation times given that the ligand shell is rich in nuclear spins and non-rigid.

Isolation of a Square-Planar Th(III) Complex: Synthesis and Structure of [Th(OC6H2tBu2-2,6-Me-4)4]1.

Reduction of Th(OC6H2tBu2-2,6-Me-4)4 using either KC8 or Li in THF forms a new example of a crystallographically characterizable Th(III) complex in the salts [K(THF)5(Et2O)][Th(OC6H2tBu2-2,6-Me-4)4] and [Li(THF)4][Th(OC6H2tBu2-2,6-Me-4)4]. Surprisingly, in each structure the four aryloxide ligands are arranged in a square-planar geometry, the first example of this coordination mode for an f element complex. The Th(III) ion and four oxygen donor atoms are coplanar to within 0.05 Å with O-Th-O angles of 89.27(8) to 92.02(8)° between cis ligands. The ligands have Th-O-C(ipso) angles of 173.9(2) to 178.6(4)°, and the aryl rings make angles of 58.5 to 65.1° with the ThO4 plane. The effect of the eight tert-butyl substituents in generating the unusual structure through packing and/or dispersion forces is discussed. EPR spectroscopy reveals an axial signal consistent with a metal-based radical in a planar complex. DFT calculations yield a C4-symmetric structure that accommodates a low-lying SOMO of 6dz2 character with 7s Rydberg admixture.

Isolation of reactive Ln(ii) complexes with C5H4Me ligands (CpMe) using inverse sandwich countercations: synthesis and structure of [(18-crown-6)K(µ-CpMe)K(18-crown-6)][CpMe3LnII] (Ln = Tb, Ho).

Although attempts to make the Y(ii) complex, (CpMe3Y)1- (CpMe = C5H4Me), by reduction of CpMe3Y with potassium were unsuccessful and the products of potassium reduction of CpMe3Ln for Ln = La and Pr led to ring-opening reduction of THF, we report that crystallographically-characterizable Ln(ii) complexes of Tb and Ho can be isolated by reducing CpMe3Ln(THF) with KC8 in THF in the presence of 18-crown-6 (18-c-6). X-ray crystallography revealed that these complexes are isolated with a methylcyclopentadienide inverse sandwich countercation: [(18-c-6)K(µ-CpMe)K(18-c-6)][CpMe3Ln] (Ln = Tb, Ho). Although reduction of CpMe3Ln with potassium in the presence of the 2.2.2-cryptand (crypt) chelate has not generally provided fully-characterizable, crystalline products, in the case of Dy, crystals of [K(crypt)][CpMe3Dy] could be isolated.

Chelate-Free Synthesis of the U(II) Complex, [(C5H3(SiMe3)2)3U]1-, Using Li and Cs Reductants and Comparative Studies of La(II) and Ce(II) Analogs.

To expand the range of synthetic options for generating complexes of the actinide metals in the +2 oxidation state, reduction of Cp″3U (Cp″ = C5H3(SiMe3)2) and the lanthanide analogs, Cp″3La and Cp″3Ce with lithium in the absence of crown ether and cryptand chelates was explored. In each case, crystallographically characterizable [Li(THF)4][Cp″3M] complexes were obtainable in yields of 70-75% for M = La and Ce and 45-50% for M = U, that is, chelating agents are not necessary to sequester the lithium countercation to form isolable crystalline M(II) products. Reductions using Cs were also explored and X-ray crystallography revealed the formation of an oligomeric structure, [Cp″U(µ-Cp")2Cs(THF)2] n, involving Cp″ ligands that bridge "(Cp″UII)1+" moieties to "[Cp″2Cs(THF)2]1-" units.

Synthesis of uranium-in-cryptand complexes.

The facile encapsulation of U(iii) and La(iii) by 2.2.2-cryptand (crypt) using simple starting materials is described. Addition of crypt to UI3 and LaCl3 forms the crystallographically-characterizable complexes, [U(crypt)I2]I and [La(crypt)Cl2]Cl. In the presence of water, the U(iii)-aquo adducts, [U(crypt)I(OH2)][I]2 and [U(crypt)I(OH2)][I][BPh4], can be isolated.

Utility of Lithium in Rare-Earth Metal Reduction Reactions to Form Nontraditional Ln2+ Complexes and Unusual [Li(2.2.2-cryptand)]1+ Cations.

The utility of lithium compared to other alkali metals in generating Ln2+ rare-earth metal complexes via reduction of Ln3+ precursors in reactions abbreviated as LnA3/M (Ln = rare-earth metal; A = anionic ligand; M = alkali metal) is described. Lithium reduction of Cp'3Ln (Cp' = C5H4SiMe3; Ln = Y, Tb, Dy, Ho) under Ar in the presence of 2.2.2-cryptand (crypt) forms new examples of crystallographically characterizable Ln2+ complexes of these metals, [Li(crypt)][Cp'3Ln]. In each complex, lithium is found in an N2O4 donor atom coordination geometry that is unusual for the cryptand ligand. Magnetic susceptibility data on these new examples of nontraditional divalent lanthanide complexes are consistent with 4fn5d1 electronic configurations. The Dy and Ho complexes have exceptionally high single-ion magnetic moments, 11.35 and 11.67 µB, respectively. Lithium reduction of Cp'3Y under N2 at -35 °C forms the Y2+ complex (Cp'3Y)1-, which reduces dinitrogen upon warming to room temperature to generate the (N2)2- complex [Cp'2Y(THF)]2(µ-η2:η2-N2). These results provide insight on the factors that lead to reduced dinitrogen complexes and/or stable divalent lanthanide complexes as a function of the specific reducing agent and conditions.

Synthesis of rare-earth-metal-in-cryptand dications, [Ln(2.2.2-cryptand)]2+, from Sm2+, Eu2+, and Yb2+ silyl metallocenes (C5H4SiMe3)2Ln(THF)2.

Cp'2Ln(THF)2 metallocenes (Cp' = C5H4SiMe3) react with 2.2.2-cryptand (crypt) to form Ln2+-in-crypt complexes, [Ln(crypt)(THF)][Cp'3Ln]2 (Ln = Sm, Eu) and [Yb(crypt)][Cp'3Yb]2, that contain Ln2+ ions surrounded only by neutral ligands. A bimetallic, mixed-ligand metallocene/opened-crypt complex of Sm2+, [Sm(C16H32N2O6-κ2O:κ2O')SmCp''2], was obtained by KC8 reduction of Cp''2Sm(THF) [Cp'' = C5H3(SiMe3)2] in the presence of crypt.