Cage Match: Comparing the Anion Binding Ability of Isostructural Versus Isofunctional Pairs of Metal-Organic Nanocages.

Affinities of six anions (mesylate, acetate, trifluoroacetate, p-toluenecarboxylate, p-toluenesulfonate, and perfluorooctanoate) for three related Pt2+ -linked porphyrin nanocages were measured to probe the influence of different noncovalent recognition motifs (e. g., hydrogen bonding, electrostatics, π bonding) on anion binding. Two new hosts of M6 L3 12+ (1b) and M4 L2 8+ (2) composition (M=(en)Pt2+ , L=(3-py)4 porphyrin) were prepared in a one-pot synthesis and allowed comparison of hosts that differ in structure while maintaining similar N-H hydrogen-bond donor ability. Comparisons of isostructural hosts that differ in hydrogen-bonding ability were made between 1b and a related M6 L3 12+ nanoprism (1a, M=(tmeda)Pt2+ ) that lacks N-H groups. Considerable variation in association constants (K1 =1.6×103  M-1 to 1.3×108  M-1 ) and binding mode (exo vs. endo) were found for different host-guest combinations. Strongest binding was seen between p-toluenecarboxylate and 1b, but surprisingly, association of this guest with 1a was only slightly weaker despite the absence of NH⋅⋅⋅O interactions. The high affinity between p-toluenecarboxylate and 1a could be turned off by protonation, and this behavior was used to toggle between the binding of this guest and the environmental pollutant perfluorooctanoate, which otherwise has a lower affinity for the host.

Metal-Ligand Proton Tautomerism, Electron Transfer, and C(sp3)-H Activation by a 4-Pyridinyl-Pincer Iridium Hydride Complex.

The para-N-pyridyl-based PCP pincer proligand 3,5-bis(di-tert-butylphosphinomethyl)-2,6-dimethylpyridine (pN-tBuPCP-H) was synthesized and metalated to give the iridium complex (pN-tBuPCP)IrHCl (2-H). In marked contrast with its phenyl-based congeners, e.g., (tBuPCP)IrHCl and derivatives, 2-H is highly air-sensitive and reacts with oxidants such as ferrocenium, trityl cation, and benzoquinone. These oxidations ultimately lead to intramolecular activation of a phosphino-t-butyl C(sp3)-H bond and cyclometalation. Considering the greater electronegativity of N than C, 2-H is expected to be less easily oxidized than simple PCP derivatives; cyclic voltammetry and DFT calculations support this expectation. However, 2-H is calculated to undergo metal-ligand-proton tautomerism (MLPT) to give an N-protonated complex that can be described with resonance forms representing a zwitterionic complex (with a negative charge on Ir) and a p-N-pyridylidene (a remote N-heterocyclic carbene) Ir(I) complex. One-electron oxidation of this tautomer is calculated to be dramatically more favorable than direct oxidation of 2-H (ΔΔG° = -31.3 kcal/mol). The resulting Ir(II) oxidation product is easily deprotonated to give metalloradical 2• which is observed by NMR spectroscopy. 2• can be further oxidized to give cationic Ir(III) complex, 2+, which can oxidatively add a phosphino-t-butyl C-H bond and undergo deprotonation to give the observed cyclometalated product. DFT calculations indicate that less sterically hindered analogues of 2+ would preferentially undergo intermolecular addition of C(sp3)-H bonds, for example, of n-alkanes. The resulting iridium alkyl complexes could undergo facile ß-H elimination to afford olefin, thereby completing a catalytic cycle for alkane dehydrogenation driven by one-electron oxidation and deprotonation, enabled by MLPT.

Controlling Intramolecular and Intermolecular Electronic Coupling of Radical Ligands in a Series of Cobaltoviologen Complexes.

Controlling electronic coupling between multiple redox sites is of interest for tuning the electronic properties of molecules and materials. While classic mixed-valence (MV) systems are highly tunable, e.g., via the organic bridges connecting the redox sites, metal-bridged MV systems are difficult to control because the electronics of the metal cannot usually be altered independently of redox-active moieties embedded in its ligands. Herein, this limitation was overcome by varying the donor strengths of ancillary ligands in a series of cobalt complexes without directly perturbing the electronics of viologen-like redox sites bridged by the cobalt ions. The cobaltoviologens [1X-Co]n+ feature four 4-X-pyridyl donor groups (X = CO2Me, Cl, H, Me, OMe, NMe2) that provide gradual electronic tuning of the bridging CoII centers, while a related complex [2-Co]n+ with NHC donors supports exclusively CoIII states even upon reduction of the viologen units. Electrochemistry and IVCT band analysis indicate that the MV states of these complexes have electronic structures ranging from fully localized ([2-Co]4+; Robin-Day Class I) to fully delocalized ([1CO2Me-Co]3+; Class III) descriptions, demonstrating unprecedented control over electronic coupling without changing the identity of the redox sites or bridging metal. Additionally, single-crystal XRD characterization of the homovalent complexes [1H-Co]2+ and [1H-Zn]2+ revealed radical-pairing interactions between the viologen ligands of adjacent complexes, representing a type of through-space electronic coupling commonly observed for organic viologen radicals but never before seen in metalloviologens. The extended solid-state packing of these complexes produces 3D networks of radical π-stacking interactions that impart unexpected mechanical flexibility to these crystals.

Two-Electron Redox Tuning of Cyclopentadienyl Cobalt Complexes Enabled by the Phenylenediamide Ligand.

Achieving multielectron activity at first-row transition-metal complexes has important implications for homogeneous catalysis using earth-abundant metals. Here, we report a family of cobalt-phenylenediamide complexes that undergo reversible 2e- oxidation regardless of the ligand substituents, enabling unprecedented multielectron redox tuning over 0.5 V and, in each case, affording the dicationic Co(III)-benzoquinonediimine species. The neutral complexes are best described as delocalized systems with π-bonding in the metallocycle, consistent with a closed-shell singlet ground state predicted by density functional theory (DFT) calculations. Our DFT results also predict an ECE pathway for 2e- oxidation (ECE = electrochemical step, chemical step, electrochemical step), where the first 1e- step involves redox-induced electron transfer to yield a Co(II) intermediate. Disruption of the metallocycle bonding in this state enables a change in the coordination geometry through association of an addition ligand, which is critical for accessing the potential inversion. The electronic properties of the phenylenediamide ligand govern whether the second electron is lost from the ligand or metal, providing a remarkable example of tunable 2e- behavior at first-row systems.

A Bis(imidazole)-based cysteine labeling tool for metalloprotein assembly.

Precise metal-protein coordination by design remains a considerable challenge. Polydentate, high-metal-affinity protein modifications, both chemical and recombinant, can enable metal localization. However, these constructs are often bulky, conformationally and stereochemically ill-defined, or coordinately saturated. Here, we expand the biomolecular metal-coordination toolbox with the irreversible attachment to cysteine of bis(1-methylimidazol-2-yl)ethene ("BMIE"), which generates a compact imidazole-based metal-coordinating ligand. Conjugate additions of small-molecule thiols (thiocresol and N-Boc-Cys) with BMIE confirm general thiol reactivity. The BMIE adducts are shown to complex the divalent metal ions Cu++ and Zn++ in bidentate (N2) and tridentate (N2S*) coordination geometries. Cysteine-targeted BMIE modification (>90% yield at pH 8.0) of a model protein, the S203C variant of carboxypeptidase G2 (CPG2), measured with ESI-MS, confirms its utility as a site-selective bioconjugation method. ICP-MS analysis confirms mono-metallation of the BMIE-modified CPG2 protein with Zn++, Cu++, and Co++. EPR characterization of the BMIE-modified CPG2 protein reveals the structural details of the site selective 1:1 BMIE-Cu++ coordination and symmetric tetragonal geometry under physiological conditions and in the presence of various competing and exchangeable ligands (H2O/HO-, tris, and phenanthroline). An X-ray protein crystal structure of BMIE-modified CPG2-S203C demonstrates that the BMIE modification is minimally disruptive to the overall protein structure, including the carboxypeptidase active sites, although Zn++ metalation could not be conclusively discerned at the resolution obtained. The carboxypeptidase catalytic activity of BMIE-modified CPG2-S203C was also assayed and found to be minimally affected. These features, combined with ease of attachment, define the new BMIE-based ligation as a versatile metalloprotein design tool, and enable future catalytic and structural applications.

Ruthenium Complexes of a Triphosphorus-Coordinating Pincer Ligand: Ru-P Ligand-Substituent Exchange Reactions Driven by Large Variations of Bond Energies.

The reaction of [(p-cymene)RuCl2]2 with the triphosphine ligand bis(2-di-tert-butylphosphinophenyl)phosphine (tBuPHPP) results in an unusual exchange reaction in which a chloride ligand and a phosphorus-bound H atom are exchanged ("H-P/Ru-Cl exchange") to give the (chlorophosphine)ruthenium hydride complex (tBuPClPP)RuHCl [1Cl-HCl; tBuPClPP = bis(2-di-tert-butylphosphinophenyl)chlorophosphine]. Density functional theory calculations indicate that the presumed initial product of metalation, (tBuPHPP)RuCl2 (1H-Cl2), undergoes an H-P/Ru-Cl exchange via sequential P-to-Ru α-H migration to give the intermediate (tBuPPP)RuHCl2, followed by Ru-to-P α-Cl migration to give the observed product 1Cl-HCl (crystallographically characterized). Dehydrochlorination of 1Cl-HCl under a H2 atmosphere gives (tBuPClPP)RuH4 (1Cl-H4), which then can undergo a second dehydrochlorination and addition of H2 to give (tBuPHPP)RuH4 (1H-H4). This reaction may proceed via the reverse of the intramolecular exchange by 1H-Cl2, i.e., loss of H2 from 1Cl-H4 to give 1Cl-H2, which could undergo Cl-P/Ru-H exchange to give (tBuPHPP)RuHCl (1H-HCl). Accordingly, the thermodynamics of Cl-P/Ru-H exchange are found to be highly dependent on the nature of the ancillary anionic ligand (H or Cl), which is not directly involved in the exchange. The origin of this thermodynamic dependence can be explained in terms of the high stability of complexes (RPXPP)RuHCl (X = H, Cl; R = Me, tBu), in which the hydride is approximately trans to a vacant coordination site and the central phosphine group is approximately trans to the weak-trans-influence chloride ligand. This conclusion has general implications for five-coordinate d6 complexes, both pincer- and nonpincer-ligated.

Synthesis of [60]- and [70]Fullerene-Fused Tetrahydroquinoxaline Derivatives by Oxidative [4 + 2] Cycloaddition with Unusual Reactivity and Regioselectivity.

The oxidative [4 + 2] reaction of o-phenylenediamine-derived disulfonamides with fullerene C60 and C70 is reported, in which electron-deficient reactants showed high reactivity. The reaction of C70 exhibited unusual regioselectivity, yielding a [5,6]-adduct as the major product, which was characterized by 1H, 13C NMR and single-crystal X-ray diffraction. DFT calculations revealed the reaction is an inverse-electron-demand Diels-Alder (IEDDA) reaction, and the [5,6]-adduct of C70 is a kinetic product.

Reactivity of Iridium Complexes of a Triphosphorus-Pincer Ligand Based on a Secondary Phosphine. Catalytic Alkane Dehydrogenation and the Origin of Extremely High Activity.

The selective functionalization of alkanes and alkyl groups is a major goal of chemical catalysis. Toward this end, a bulky triphosphine with a central secondary phosphino group, bis(2-di-t-butyl-phosphinophenyl)phosphine (tBuPHPP), has been synthesized. When complexed to iridium, it adopts a meridional ("pincer") configuration. The secondary phosphino H atom can undergo migration to iridium to give an anionic phosphido-based-pincer (tBuPPP) complex. Stoichiometric reactions of the (tBuPPP)Ir complexes reflect a distribution of steric bulk around the iridium center in which the coordination site trans to the phosphido group is quite crowded; one coordination site cis to the phosphido is even more crowded; and the remaining site is particularly open. The (tBuPPP)Ir precursors are the most active catalysts reported to date for dehydrogenation of n-alkanes, by about 2 orders of magnitude. The electronic properties of the iridium center are similar to that of well-known analogous (RPCP)Ir catalysts. Accordingly, DFT calculations predict that (tBuPPP)Ir and (tBuPCP)Ir are, intrinsically, comparably active for alkane dehydrogenation. While dehydrogenation by (RPCP)Ir proceeds through an intermediate trans-(PCP)IrH2(alkene), (tBuPPP)Ir follows a pathway proceeding via cis-(PPP)IrH2(alkene), thereby circumventing unfavorable placement of the alkene at the bulky site trans to phosphorus. (tBuPPP)Ir and (tBuPCP)Ir, however, have analogous resting states: square planar (pincer)Ir(alkene). Alkene coordination at the crowded trans site is therefore unavoidable in the resting states. Thus, the resting state of the (tBuPPP)Ir catalyst is destabilized by the architecture of the ligand, and this is largely responsible for its unusually high catalytic activity.

Isocyanide-Induced Annulation Leading to Cyclopento-, Methano-, and Cyclopentano-[60]Fullerene Derivatives.

The three-component annulation reactions of C60, alkyl isocyanide, and dimethyl acetylenedicarboxylate (DMAD) or unsymmetric alkynes are investigated to afford cyclopent-2-en-1-imino- and ketenimine methano-[60]fullerene derivatives, which, upon hydration in the presence of acid, yield the corresponding fullerene amides. Dimethyl 2,3-pentadienedioate, the allene counterpart of DMAD, and ethyl buta-2,3-dienoate undergo four-component annulation with C60, alkyl isocyanide, and water under similar conditions to yield cyclopentano-[60]fullerene derivatives with similar amide groups.

Unexpected Formation of Metallofulleroids from Multicomponent Reactions, with Crystallographic and Computational Studies of the Cluster Motion.

New multicomponent reactions involving an isocyanide, terminal or internal alkynes, and endohedral metallofullerene (EMF) Lu3 N@C80 yield metallofulleroids which are characterized by mass-spectrometry, HPLC, and multiple 1D and 2D NMR techniques. Single crystal studies revealed one ketenimine metallofulleroid has ordered Lu3 N cluster which is unusual for EMF monoadducts. Computational analysis, based on crystallographic data, confirm that the endohedral cluster motion is controlled by the position of the exohedral organic appendants. Our findings provide a new functionalization reaction for EMFs, and a potential facile approach to freeze the endohedral cluster motion at relatively high temperatures.

Insights into Formate Oxidation by a Series of Cobalt Piano-Stool Complexes Supported by Bis(phosphino)amine Ligands.

A series of (cyclopentadienyl)cobalt(III) half-sandwich complexes (1-4) supported by bidentate bis(phosphino)amine ligands was synthesized and characterized by NMR spectroscopy, X-ray crystallography, and cyclic voltammetry. The CoIII-hydride complex 4-H bearing the bis(cyclohexylphosphine) ligand derivative was successfully isolated via protonation of the neutral reduced CoI complex 5 with a weak acid. Experimental and computational methods were used to determine the thermodynamic hydride accepting ability of these CoIII centers and to evaluate their reactivity toward the oxidation of formate. We find that the hydride accepting ability of 1-4 ranges from 71 to 74 kcal/mol in acetonitrile, which should favor a highly exergonic reaction with formate through direct hydride transfer. Formate oxidation was demonstrated at elevated temperatures in the presence of stoichiometric quantities of 4, generating carbon dioxide and the CoIII-hydride complex 4-H in 72% yield.

Stereoelectronic Features of a Complex Ketene Dimerization Reaction.

The amidation reaction of a tetrahydroisoquinolin-1-one-4-carboxylic acid is a key step in the multi-kilogram-scale preparation of the antimalarial drug SJ733, now in phase 2 clinical trials. In the course of investigating THIQ carboxamidations, we found that propanephosphonic acid anhydride (T3P) is an effective reagent, although the yield and byproducts vary with the nature and quantity of the base. As a control, the T3P reaction of a 3-(2-thienyl) THIQ was performed in the absence of the amine, and the products were characterized: among them are three dimeric allenes and two dimeric lactones. A nucleophile-promoted ketene dimerization process subject to subtle steric and stereoelectronic effects accounts for their formation. Two novel monomeric products, a decarboxylated isoquinolone and a purple, fused aryl ketone, were also isolated, and mechanisms for their formation from the ketene intermediate are proposed.

Crystallizing Atomic Xenon in a Flexible MOF to Probe and Understand Its Temperature-Dependent Breathing Behavior and Unusual Gas Adsorption Phenomenon.

Flexible metal-organic frameworks (MOFs) hold great promise as smart materials for specific applications such as gas separation. These materials undergo interesting structural changes in response to guest molecules, which is often associated with unique adsorption behavior not possible for rigid MOFs. Understanding the dynamic behavior of flexible MOFs is crucial yet challenging as it involves weak host-guest interactions and subtle structural transformation not only at the atomic/molecular level but also in a nonsteady state. We report here an in-depth study on the adsorbate- and temperature-dependent adsorption in a flexible MOF by crystallizing atomic gases into its pores. Mn(ina)2 shows an interesting temperature-dependent response toward noble gases. Its nonmonotonic, temperature-dependent adsorption profile results in an uptake maximum at a temperature threshold, a phenomenon that is unusual. Full characterization of Xe-loaded MOF structures is performed by in situ single-crystal and synchrotron X-ray diffraction, IR spectroscopy, and molecular modeling. The X-ray diffraction analysis offers a detailed explanation into the dynamic structural transformation and provides a convincing rationalization of the unique adsorption behavior at the molecular scale. The guest and temperature dependence of the structural breathing gives rise to an intriguing reverse of Xe/Kr adsorption selectivity as a function of temperature. The presented work may provide further understanding of the adsorption behavior of noble gases in flexible MOF structures.

Evaluation of 1,1-cyclopropylidene as a thioether isostere in the 4-thio-thienopyrimidine (TTP) series of antimalarials.

The 4-(heteroarylthio)thieno[2,3-d]pyrimidine (TTP) series of antimalarials, represented by 1 and 17, potently inhibit proliferation of the 3D7 strain of P. falciparum (EC50 70-100 nM), but suffer from oxidative metabolism. The 1,1-cyclopropylidene isosteres 6 and 16 were designed to obviate this drawback. They were prepared by a short route that features a combined Peterson methylenation / cyclopropanation transformation of, e. g., ketone 7. Isosteres 6 and 16 possess significantly attenuated antimalarial potency relative to parents 1 and 17. This outcome can be rationalized based on the increased out-of-plane steric demands of the latter two. In support of this hypothesis, the relatively flat ketone 7 retains some of the potency of 1, even though it appears to be a comparatively inferior mimic with respect to electronics and bond lengths and angles. We also demonstrate crystallographically and computationally an apparent increase in the strength of the intramolecular sulfur hole interaction of 1 upon protonation.

Ambient and High Pressure CuNiSb2: Metal-Ordered and Metal-Disordered NiAs-Type Derivative Pnictides.

The mineral Zlatogorite, CuNiSb2, was synthesized in the laboratory for the first time by annealing elements at ambient pressure (CuNiSb2-AP). Rietveld refinement of synchrotron powder X-ray diffraction data indicates that CuNiSb2-AP crystallizes in the NiAs-derived structure (P3m1, #164) with Cu and Ni ordering. The structure consists of alternate NiSb6 and CuSb6 octahedral layers via face-sharing. The formation of such structure instead of metal disordered NiAs-type structure (P63/mmc, #194) is validated by the lower energy of the ordered phase by first-principle calculations. Interatomic crystal orbital Hamilton population, electron localization function, and charge density analysis reveal strong Ni-Sb, Cu-Sb, and Cu-Ni bonding and long weak Sb-Sb interactions in CuNiSb2-AP. The magnetic measurement indicates that CuNiSb2-AP is Pauli paramagnetic. First-principle calculations and experimental electrical resistivity measurements reveal that CuNiSb2-AP is a metal. The low Seebeck coefficient and large thermal conductivity suggest that CuNiSb2 is not a potential thermoelectric material. Single crystals were grown by chemical vapor transport. The high pressure sample (CuNiSb2-8 GPa) was prepared by pressing CuNiSb2-AP at 700 °C and 8 GPa. However, the structures of single crystal and CuNiSb2-8 GPa are best fit with a disordered metal structure in the P3m1 space group, corroborated by transmission electron microscopy.

The Influence of Redox-Active Linkers on the Stability and Physical Properties of a Highly Electroactive Porphyrin Nanoprism.

Redox-active metal-organic nanocages are of interest for many applications, but the development of cages with extensive redox activity is often hindered by their limited stability and solubility across multiple charge states. This report reveals that these properties can be tuned for cages with redox-active walls by incorporating additional redox activity into the linkers. In particular, new +12 charged triangular nanoprisms 1a,b were formed from three electroactive tetrakis(3-pyridyl)porphyrin walls linked by six [(TMEDA)Pt]2+ (for 1a) or [(2,2'-bipy)Pt]2+ (for 1b) vertices, the latter of which are also electroactive. Thus, 1b exhibits extensive redox activity, consisting of two porphyrin-centered (x3) and two 2,2'-bipy-centered (x6) reductions that provide reversible access to +12, +9, +3, 0, and -6 charge states, whereas 1a undergoes only two, porphyrin-centered (x3) reversible reductions. Comparisons of 1a and 1b (and monomeric control compounds) by cyclic voltammetry and UV-vis-NIR spectroelectrochemistry show that the redox-activity of the linkers in 1b lowers the second reduction potential of the porphyrins by 100 mV and improves the stability and solubility of this structure under highly reducing conditions (e.g., -2.25 V vs Fc+/0 in MeCN). These findings reveal new principles for controlling the properties of highly electroactive molecular nanostructures. Anion exchange rates (≫103 s-1) were also probed, showing that the narrow apertures (≤3 Å van der Waals width) of 1a,b do not impede the loss/gain of PF6- anions during redox processes.

Identification of the local electrical properties of crystalline and amorphous domains in electrochemically doped conjugated polymer thin films.

Doped polymer thin films have several applications in electronic, optoelectronic and thermoelectric devices. Often the electrical properties of doped conjugated polymer thin films are affected by their local physical and mechanical characteristics. However, investigations into the effects of doping on local domain properties have not been carried out. Here, we study the physical, mechanical and optical properties of electrochemically doped P3HT thin films at the nanoscale and establish a relation between doping level and the physical properties of P3HT thin films. Bulk crystallinity of both pristine and doped P3HT thin films, characterized using grazing incidence X-ray diffraction, shows a clear loss in crystallinity upon doping. Nanoscale crystalline and amorphous domains in the films are visualized by multimode atomic force microscopy (AFM). It is apparent that the crystalline domains are most affected by doping and have a higher degree of doping compared to amorphous domains. This results in crystalline domains exhibiting superior electrical conductivity at a local level. These results are further supported by Raman mapping and elemental analysis of doped films. A direct relation is established between the physical, mechanical and electrical properties of doped P3HT thin films based on the AFM data. The findings demonstrate that higher dopant concentrations are found in crystalline domains compared to amorphous domains, which has not been shown before to the best of our knowledge. This study can be used to optimize the electronic properties of doped P3HT thin films for use in electronic and optoelectronic device applications.

Molecular Thorium Compounds with Dichalcogenide Ligands: Synthesis, Structure, 77Se NMR Study, and Thermolysis.

A series of dimeric thorium disulfides and diselenides have been prepared with sterically undemanding ancillary ligands. Five complexes, (py)6Th2I4(µ2-S2)2, (py)6Th2Br2(SC6F5)2(µ2-S2)2, (py)6Th2I4(µ2-Se2)2, (py)6Th2I2(SC6F5)2(µ2-Se2)2, and (py)6Th2Br2(SC6F5)2(µ2-Se2)2, were isolated in high yields by first reducing mixtures of I2, F5C6SSC6F5, PhSeSePh, or PhSSPh, and PhSeBr with elemental Th, followed by in situ ligand-based redox reactions with elemental sulfur or selenium. These are the first examples of thorium compounds with bridging dichalcogenide ligands. Attempts to prepare chloride derivatives gave mixtures of (py)4ThCl4 and either (py)6Th2Cl2(SC6F5)2(µ2-S2)2 or (py)8Th4Se4(SePh)4(SC6F5)4. All products were characterized by single-crystal and powder X-ray diffraction and IR, UV-visible, and NMR spectroscopy. A computational analysis of experimental 77Se NMR chemical shifts reveals that the solvated dimeric structures with two bridging dichalcogenides are maintained in solution. Thermolysis of (py)6Th2I4(µ2-Se2)2 leads to reduction of the bridging Se22- moieties, oxidation of the I- ligand, and formation of solid-state ThSe2 and I2.

Monomeric thorium chalcogenolates with bipyridine and terpyridine ligands.

Thorium chalcogenolates Th(ER)4 react with 2,2'-bipyridine (bipy) to form complexes with the stoichiometry (bipy)2Th(ER)4 (E = S, Se; R = Ph, C6F5). All four compounds have been isolated and characterized by spectroscopic methods and low-temperature single crystal X-ray diffraction. Two of the products, (bipy)2Th(SC6F5)4 and (bipy)2Th(SeC6F5)4, crystallize with lattice solvent, (bipy)2Th(SPh)4 crystallizes with no lattice solvent, and the selenolate (bipy)2Th(SePh)4 crystallizes in two phases, with and without lattice solvent. In all four compounds the available volume for coordination bounded by the two bipy ligands is large enough to allow significant conformational flexibility of thiolate or selenolate ligands. 77Se NMR confirms that the structures of the selenolate products are the same in pyridine solution and in the solid state. Attempts to prepare analogous derivatives with 2,2',6',2''-terpyridine (terpy) were successful only in the isolation of (terpy)(py)Th(SPh)4, the first terpy compound of thorium. These materials are thermochromic, with color attributed to ligand-to-ligand charge transfer excitations.

Organosoluble tetravalent actinide di- and trifluorides.

Soluble molecular actinide(iv) fluorides can be prepared in high yield via redox or metathesis reactions of silver fluorides with actinide compounds containing ancillary iodide or fluorinated thiolate ligands. Two compounds, (py)4UF2I2·2py and (py)7Th2F5(SC6F5)3·2py were isolated and characterized by conventional methods, powder and low temperature single crystal X-ray diffraction.