Nonaqueous Electrochemistry of Uranium Complexes: A Guide to Structure-Reactivity Tuning.

Uranium complexes can be stabilized in a wide range of oxidation states, ranging from UII to UVI and a very recent example of a UI complex. This review provides a comprehensive summary of electrochemistry data reported on uranium complexes in nonaqueous electrolyte, to serve as a clear point of reference for newly synthesized compounds, and to evaluate how different ligand environments influence experimentally observed electrochemical redox potentials. Data for over 200 uranium compounds are reported, together with a detailed discussion of trends observed across larger series of complexes in response to ligand field variations. In analogy to the traditional Lever parameter, we utilized the data to derive a new uranium-specific set of ligand field parameters UEL(L) that more accurately represent metal-ligand bonding situations than previously existing transition metal derived parameters. Exemplarily, we demonstrate UEL(L) parameters to be useful for the prediction of structure-reactivity correlations in order to activate specific substrate targets.

A Vanadium Methylidene.

Examples of stable 3d transition metal methylidene complexes are extremely rare. Here we report an isolable and stable vanadium methylidene complex, [(PNP)V(=NAr)(=CH2)] (PNP = N[2-PiPr2-4-methylphenyl]-, Ar = 2,6-iPr2C6H3), via H atom transfer (HAT) from [(PNP)V(NHAr)(CH3)] or [(PNP)V(=NAr)(CH3)] using two or one equivalents of the TEMPO radical (TEMPO = (2,2,6,6-tetramethylpiperidin-1-yl)oxyl), respectively. Alternatively, the vanadium methylidene moiety can also be formed via the treatment of transient [(PNP)V=NAr] with the Wittig reagent, H2CPPh3. Structural and spectroscopic analysis, including 13C enriched labeling of the methylidene ligand, unequivocally confirmed the terminal nature of a rare 3d methylidene complex, featuring a V=CH2 bond distance of 1.908(2) Å and a highly downfield 13C NMR spectral shift at 298 ppm. In the absence of the ylide, intermediate [(PNP)V=NAr] activates dinitrogen to form an end-on bridging N2 complex, [(PNP)V(=NAr)]2(µ2-η1:η1-N2), having a singlet ground state. Complex [(PNP)V(=NAr)(=CH2)] reacts with H3COTf to form [(PNP)V(=NAr)(OTf)], accompanied by the release of ethylene as evidenced by 1H NMR spectroscopy, and reactivity studies suggest a ß-hydride elimination pathway.

A bis-Phenolate Carbene-Supported bis-µ-Oxo Iron(IV/IV) Complex with a [FeIV(µ-O)2FeIV] Diamond Core Derived from Dioxygen Activation.

The diiron(II) complex, [(OCO)Fe(MeCN)]2 (1, MeCN = acetonitrile), supported by the bis-phenolate carbene pincer ligand, 1,3-bis(3,5-di-tert-butyl-2-hydroxyphenyl)benzimidazolin-2-ylidene (OCO), was synthesized and characterized by single-crystal X-ray diffraction, 1H nuclear magnetic resonance, infrared (IR) vibrational, ultraviolet/visible/near-infrared (UV/vis/NIR) electronic absorption, 57Fe Mössbauer, X-band electron paramagnetic resonance (EPR) and SQUID magnetization measurements. Complex 1 activates dioxygen to yield the diferric, µ-oxo-bridged complex [(OCO)Fe(py)(µ-O)Fe(O(C═O)O)(py)] (2) that was isolated and fully characterized. In 2, one of the iron-carbene bonds was oxidized to give a urea motif, resulting in an O(CNHC═O)O binding site, while the other Fe(OCO) unit remained unchanged. When the reaction is performed at -80 °C, an intensively colored, purple intermediate is observed (INT, λmax = 570 nm; ε = 5600 mol L-1 cm-1). INT acts as a sluggish oxidant, reacting only with easily oxidizable substrates, such as PPh3 or 2-phenylpropionic aldehyde (2-PPA). The identity of INT can be best described as a dinuclear complex containing a closed diamond core motif [(OCO)FeIV(µ-O)2FeIV(OCO)]. This proposal is based on extensive spectroscopic [UV/vis/NIR electronic absorption, 57Fe Mössbauer, X-band EPR, resonance Raman (rRaman), X-ray absorption, and nuclear resonance vibrational (NRVS)] and computational studies. The conversion of the diiron(II) complex 1 to the oxo diiron(IV) intermediate INT is reminiscent of the O2 activation process in soluble methane monooxygenases (sMMO). Most importantly, the low reactivity of INT supports the consensus that the [FeIV(µ-O)2FeIV] diamond core in sMMO is kinetically inert and needs to open up to terminal FeIV═O cores to react with the strong C-H bonds of methane.

Softer Is Better for Titanium: Molecular Titanium Arsenido Anions Featuring Ti≡As Bonding and a Terminal Parent Arsinidene.

We introduce the arsenido ligand onto the TiIV ion, yielding a remarkably covalent Ti≡As bond and the parent arsinidene Ti═AsH moiety. An anionic arsenido ligand is assembled via reductive decarbonylation involving the discrete TiII salt [K(cryptand)][(PN)2TiCl] (1) (cryptand = 222-Kryptofix) and Na(OCAs)(dioxane)1.5 in thf/toluene to produce the mixed alkali ate-complex [(PN)2Ti(As)]2(µ2-KNa(thf)2) (2) and the discrete salt [K(cryptand)][(PN)2Ti≡As] (3) featuring a terminal Ti≡As ligand. Protonation of 2 or 3 with various weak acids cleanly forms the parent arsinidene [(PN)2Ti═AsH] (4), which upon deprotonation with KCH2Ph in thf generates the more symmetric anionic arsenido [(PN)2Ti(As){µ2-K(thf)2}]2 (5). Experimental and computational studies suggest the pKa of 4 to be ∼23, and the bond orders in 2, 3, and 5 are all in the range of a Ti≡As triple bond, with decreasing bond order in 4.

Deciphering Iron-Catalyzed C-H Amination with Organic Azides: N2 Cleavage from a Stable Organoazide Complex.

Catalytic C-N bond formation by direct activation of C-H bonds offers wide synthetic potential. En route to C-H amination, complexes with organic azides are critical precursors towards the reactive nitrene intermediate. Despite their relevance, α-N coordinated organoazide complexes are scarce in general, and elusive with iron, although iron complexes are by far the most active catalysts for C-H amination with organoazides. Herein, we report the synthesis of a stable iron α-N coordinated organoazide complex from [Fe(N(SiMe3 )2 )2 ] and AdN3 (Ad=1-adamantyl) and its crystallographic, IR, NMR and zero-field 57 Fe Mössbauer spectroscopic characterization. These analyses revealed that the organoazide is in fast equilibrium between the free and coordinated state (Keq =62). Photo-crystallography experiments showed gradual dissociation of N2 , which imparted an Fe-N bond shortening and correspond to structural snapshots of the formation of an iron imido/nitrene complex. Reactivity of the organoazide complex in solution showed complete loss of N2 , and subsequent formation of a C-H aminated product via nitrene insertion into a C-H bond of the N(SiMe3 )2 ligand. Monitoring this reaction by 1 H NMR spectroscopy indicates the transient formation of the imido/nitrene intermediate, which was supported by Mössbauer spectroscopy in frozen solution.

Self-Assembled Supported Ionic Liquids.

Separation and reuse of the catalytically active metal complexes are persistent issues in homogeneous catalysis. Supported Ionic Liquid Phase (SILP) catalysts, where the catalytic center is dissolved in a thin film of a stable ionic liquid, deposited on a solid support, present a promising alternative. However, the dissolution of the metal center in the film leaves little control over its position and its activity. We present here four novel, task-specific ionic liquids [FPhn ImH R]I (n=1, 2; R=PEG2 , C12 H25 ), designed to self-assemble on a silica surface without any covalent bonding and offering a metal binding site in a controlled distance to the support. Advanced multinuclear solid-state NMR spectroscopic techniques under Magic Angle Spinning, complemented by molecular dynamics (MD) simulations, allow us to determine their molecular conformation when deposited inside SBA-15 as a model silica support. We provide here conceptual proof for a rational design of ionic liquids self-assembling into thin films, opening an avenue for a second, improved generation of SILP catalysts.

Evolution of Surface Tension and Hansen Parameters of a Homologous Series of Imidazolium-Based Ionic Liquids.

In this study, we systematically analyze the surface tension and Hansen solubility parameters (HSPs) of imidazolium-based ionic liquids (ILs) with different anions ([NTf2]-, [PF6]-, [I]-, and [Br]-). These anions are combined with the classical 1-alkyl-3-methyl-substituted imidazolium cations ([CnC1Im]+) and a group of oligoether-functionalized imidazolium cations ([(mPEGn)2Im]+) based on methylated polyethylene glycol (mPEGn). In detail, the influences of the length of the alkyl- and the mPEGn-chain, the anion size, and the water content are investigated experimentally. For [CnC1Im]+-based ILs, the surface tension decreases with increasing alkyl chain length in all cases, but the magnitude of this decrease depends on the size of the anion ([NTf2]- < [PF6]- < [Br]- ≤ [I]-). Molecular dynamics (MD) simulations on [CnC1Im]+-based ILs indicate that these differences are caused by the interplay of charged and uncharged domains, in particular in the different anions, which affects the ability of the alkyl chains of the cation to orient toward the liquid-gas interface. An increase in the mPEGn-chain length of the [(mPEGn)2Im][A] ILs does not significantly influence the surface tension. These changes upon variation of the cation/anion combination do not correlate with the evolution of the HSPs for the two sets of ILs. Finally, our data suggest that significant water contents up to water mole fractions of x(H2O) = 0.25 do not significantly affect the surface tension of the studied binary IL-water mixtures.

From d8 to d1: Iron(0) and Iron(I) Complexes Complete the Series of Eight Fe Oxidation States within the TIMMNMes Ligand Framework.

Reduction of the ferrous precursor [(TIMMNMes)Fe(Cl)]+ (1) (TIMMNMes = tris-[(3-mesitylimidazol-2-ylidene)methyl]amine) to the low-valent iron(0) complex [(TIMMNMes)Fe(CO)3] (2) is presented, where the tris(N-heterocyclic carbene) (NHC) ligand framework remains intact, yet the coordination mode changed from 3-fold to 2-fold coordination of the carbene arms. Further, the corresponding iron(I) complexes [(TIMMNMes)Fe(L)]+ (L = free site, η1-N2, CO, py) (3) are synthesized and fully characterized. Complexes 1-3 demonstrate the notable steric and electronic flexibility of the TIMMNMes ligand framework by variation of the Fe-N anchor and Fe-carbene distances and the variable size of the axial cavity occupation. This is further underpinned by the oxidation of 3-N2 in a reaction with benzophenone to yield the corresponding, charge-separated iron(II) radical complex [(TIMMNMes)Fe(OCPh2)]+ (4). We found rather surprising similarities in the reactivity behavior when going to low- or high-valent oxidation states of the central iron ion. This is demonstrated by the closely related reactivity of 3-N2, where H atom abstraction with TEMPO triggers the formation of the metallacycle [(TIMMNMes*)Fe(py)]+ (5), and the reactivity of the highly unstable Fe(VII) nitride complex [(TIMMNMes)Fe(N)(F)]3+ to give the metallacyclic Fe(V) imido complex [(TIMMNMesN)Fe(NMes)(MeCN)]3+ (6) upon warming. Thus, the employed tris(carbene) chelate is not only capable of stabilizing the superoxidized Fe(VI) and Fe(VII) nitrides but equally supports the iron center in its low oxidation states 0 and +1. Isolation and characterization of these zero- and monovalent iron complexes demonstrate the extraordinary capability of the tris(carbene) chelate TIMMN to support iron in eight different oxidation states within the very same ligand platform.

A Caged Neutral 17-Valence-Electron Iron(I) Radical [Fe(CO)2(Cl)(P((CH2)10)3P)]•: Synthetic, Structural, Spectroscopic, Redox, and Computational Studies.

UV irradiation of yellow CH2Cl2 solutions of trans-Fe(CO)3(P((CH2)10)3P) (2a) and PMe3 (10 equiv) gives, in addition to the previously reported dibridgehead diphosphine P((CH2)10)3P (46%), a green paramagnetic complex that crystallography shows to be the trigonal-bipyramidal iron(I) radical trans-[Fe(CO)2(Cl)(P((CH2)10)3P)]• (1a•; 31% after workup). This is a rare example of an isolable species of the formula [Fe(CO)4-n(L)n(X)]• (n = 0-3, L = two-electron-donor ligand; X = one-electron-donor ligand). Analogous precursors with longer P(CH2)nP segments (n = 12, 14, 16, 18) give only the demetalated diphosphines, and a rationale is proposed. The magnetic susceptibility of 1a•, assayed by Evans' method and SQUID measurements, indicates a spin (S) of 1/2. Cyclic voltammetry shows that 1a• undergoes a partially reversible one-electron oxidation, but no facile reduction. The UV-visible, EPR, and 57Fe Mössbauer spectra are analyzed in detail. Complex 2a is similarly studied, and, despite the extra valence electron, exhibits a comparable oxidation potential (ΔE1/2 ≤ 0.04 V). The crystal structure shows a cage conformation, solvation level, disorder motif, and unit cell parameters essentially identical to those of 1a•. DFT calculations provide much insight regarding the structural, redox, and spectroscopic properties.

Benzene-1,4-Di(dithiocarboxylate) Linker-Based Coordination Polymers of Mn2+, Zn2+, and Mixed-Valence Fe2+/3.

Three new coordination polymers (CPs) constructed from the linker 1,4-di(dithiocarboxylate) (BDDTC2-)─the sulfur-analog of 1,4-benzenedicarboxylate (BDC2-)─together with Mn-, Zn-, and Fe-based inorganic SBUs are reported with description of their structural and electronic properties. Single-crystal X-ray diffraction revealed structural diversity ranging from one-dimensional chains in [Mn(BDDTC)(DMF)2] (1) to two-dimensional (2D) honeycomb sheets observed for [Zn2(BDDTC)3][Zn(DMF)5(H2O)] (2). Gas adsorption experiments confirmed a 3D porous structure for the mixed-valent material [Fe2(BDDTC)2(OH)] (3). 3 contains a 1:1 ratio of Fe2+/3+ ions, as evidenced by 57Fe Mössbauer, X-band EPR, and X-ray absorption spectroscopy. Its empirical formula was established by elemental analysis, thermal gravimetric analysis, infrared vibrational spectroscopy, and X-ray absorption spectroscopy in lieu of elusive single-crystal X-ray diffraction data. In contrast to the Mn- and Zn-based compounds 1 and 2, the Fe2+/3+ CP 3 showed remarkably high electrical conductivity of 5 × 10-3 S cm-1 (according to van der Pauw measurements), which is within the range of semiconducting materials. Overall, our study confirms that sulfur derivatives of typical carboxylate linkers (e.g., BDC) are suitable for the construction of electrically conducting CPs, due to acceptedly higher covalency in metal-ligand bonding compared to the electrically insulating carboxylate CPs or metal-organic frameworks. At the same time, the direct comparison between insulating CPs 1 and 2 with CP 3 emphasizes that the electronic structure of the metal is likewise a crucial aspect to construct electrically conductive materials.

Unlocking the Metalation Applications of TMP-powered Fe and Co(II) bis(amides): Synthesis, Structure and Mechanistic Insights.

Typified by LiTMP and TMPMgCl.LiCl, (TMP=2,2,6,6-tetramethylpiperidide), s-block metal amides have found widespread applications in arene deprotonative metalation. On the contrary, transition metal amides lack sufficient basicity to activate these substrates. Breaking new ground in this field, here we present the synthesis and full characterisation of earth-abundant transition metals M(TMP)2 (M=Fe, Co). Uncovering a new reactivity profile towards fluoroarenes, these amide complexes can promote direct M-H exchange processes regioselectively using one or two of their basic amide arms. Remarkably, even when using a perfluorinated substrate, selective C-H metalation occurs leaving C-F bonds intact. Their kinetic basicity can be boosted by LiCl or NBu4Cl additives which enables formation of kinetically activated ate species. Combining spectroscopic and structural studies with DFT calculations, mechanistic insights have been gained on how these low polarity metalation processes take place. M(TMP)2 can also be used to access ferrocene and cobaltocene by direct deprotonation of cyclopentadiene and undergo efficient CO2 insertion of both amide groups under mild reaction conditions.

Divalent Titanium via Reductive N-C Coupling of a TiIV Nitrido with π-Acids.

The nitrido-ate complex [(PN)2Ti(N){µ2-K(OEt2)}]2 (1) (PN-=(N-(2-PiPr2-4-methylphenyl)-2,4,6-Me3C6H2) reductively couples CO and isocyanides in the presence of DME or cryptand (Kryptofix222), to form rare, five-coordinate TiII complexes having a linear cumulene motif, [K(L)][(PN)2Ti(NCE)] (E=O, L=Kryptofix222, (2); E=NAd, L=3 DME, (3); E=NtBu, L=3 DME, (4); E=NAd, L=Kryptofix222, (5)). Oxidation of 2-5 with [Fc][OTf] afforded an isostructural TiIII center containing a neutral cumulene, [(PN)2Ti(NCE)] (E=O, (6); E=NAd (7), NtBu (8)) and characterization by CW X-band EPR spectroscopy, revealed unpaired electron to be metal centric. Moreover, 1e- reduction of 6 and 7 in the presence of Kryptofix222cleanly reformed corresponding discrete TiII complexes 2 and 5, which were further characterized by solution magnetization measurements and high-frequency and -field EPR (HFEPR) spectroscopy. Furthermore, oxidation of 7 with [Fc*][B(C6F5)4] resulted in a ligand disproportionated TiIV complex having transoid carbodiimides, [(PN)2Ti(NCNAd)2] (9). Comparison of spectroscopic, structural, and computational data for the divalent, trivalent, and tetravalent systems, including their 15N enriched isotopomers demonstrate these cumulenes to decrease in order of backbonding as TiII→TiIII→TiIV and increasing order of π-donation as TiII→TiIII→TiIV, thus displaying more covalency in TiIII species. Lastly, we show a synthetic cycle whereby complex 1 can deliver an N-atom to CO and CNAd.

From Divalent to Pentavalent Iron Imido Complexes and an Fe(V) Nitride via N-C Bond Cleavage.

As key intermediates in metal-catalyzed nitrogen-transfer chemistry, terminal imido complexes of iron have attracted significant attention for a long time. In search of versatile model compounds, the recently developed second-generation N-anchored tris-NHC chelating ligand tris-[2-(3-mesityl-imidazole-2-ylidene)-methyl]amine (TIMMNMes) was utilized to synthesize and compare two series of mid- to high-valent iron alkyl imido complexes, including a reactive Fe(V) adamantyl imido intermediate en route to an isolable Fe(V) nitrido complex. The chemistry toward the iron adamantyl imides was achieved by reacting the Fe(I) precursor [(TIMMNMes)FeI(N2)]+ (1) with 1-adamantyl azide to yield the corresponding trivalent iron imide. Stepwise chemical reduction and oxidation lead to the isostructural series of low-spin [(TIMMNMes)Fe(NAd)]0,1+,2+,3+ (2Ad-5Ad) in oxidation states II to V. The Fe(V) imide [(TIMMNMes)Fe(NAd)]3+ (5Ad) is unstable under ambient conditions and converts to the air-stable nitride [(TIMMNMes)FeV(N)]2+ (6) via N-C bond cleavage. The stability of the pentavalent imide can be increased by derivatizing the nitride [(TIMMNMes)FeIV(N)]+ (7) with an ethyl group using the triethyloxonium salt Et3OPF6. This gives access to the analogous series of ethyl imides [(TIMMNMes)Fe(NEt)]0,1+,2+,3+ (2Et-5Et), including the stable Fe(V) ethyl imide. Iron imido complexes exist in a manifold of different electronic structures, ultimately controlling their diverse reactivities. Accordingly, these complexes were characterized by single-crystal X-ray diffraction analyses, SQUID magnetization, and electrochemical methods, as well as 57Fe Mössbauer, IR vibrational, UV/vis electronic absorption, multinuclear NMR, X-band EPR, and X-ray absorption spectroscopy. Our studies are complemented with quantum chemical calculations, thus providing further insight into the electronic structures of all complexes.

Uranium-Mediated Peroxide Activation and a Precursor toward an Elusive Uranium cis-Dioxo Fleeting Intermediate.

The activation of chalcogen-chalcogen bonds using organometallic uranium complexes has been well documented for S-S, Se-Se, and Te-Te bonds. In stark contrast, reports concerning the ability of a uranium complex to activate the O-O bond of an organic peroxide are exceedingly rare. Herein, we describe the peroxide O-O bond cleavage of 9,10-diphenylanthracene-9,10-endoperoxide in nonaqueous media, mediated by a uranium(III) precursor [((Me,AdArO)3N)UIII(dme)] to generate a stable uranium(V) bis-alkoxide complex, namely, [((Me,AdArO)3N)UV(DPAP)]. This reaction proceeds via an isolable, alkoxide-bridged diuranium(IV/IV) species, implying that the oxidative addition occurs in two sequential, single-electron oxidations of the metal center, including rebound of a terminal oxygen radical. This uranium(V) bis-alkoxide can then be reduced with KC8 to form a uranium(IV) complex, which upon exposure to UV light, in solution, releases 9,10-diphenylanthracene to generate a cyclic uranyl trimer through formal two-electron photooxidation. Analysis of the mechanism of this photochemical oxidation via density functional theory (DFT) calculations indicates that the formation of this uranyl trimer occurs through a fleeting uranium cis-dioxo intermediate. At room temperature, this cis-configured dioxo species rapidly isomerizes to a more stable trans configuration through the release of one of the alkoxide ligands from the complex, which then goes on to form the isolated uranyl trimer complex.

Synthesis and Reactivity of a Cobalt-Supported Singlet Nitrene.

The synthesis, characterization, and reactivity of a series of cobalt terminal imido complexes supported by an N-anchored tripodal tris(carbene) chelate is described, including a Co-supported singlet nitrene. Reaction of the CoI precursor [(TIMMNmes)CoI](PF6) (TIMMNmes = tris-[2-(3-mesityl-imidazolin-2-ylidene)-methyl]amine) with p-methoxyphenyl azide yields a CoIII imide [(TIMMNmes)CoIII(NAnisole)](PF6) (1). Treatment of 1 with 1 equiv of [FeCp2](PF6) at -35 °C affords a formal CoIV imido complex [(TIMMNmes)Co(NAnisole)](PF6)2 (2), which features a bent Co-N(imido)-C(Anisole) linkage. Subsequent one-electron oxidation of 2 with 1 equiv of AgPF6 provides access to the tricationic cobalt imido complex [(TIMMNmes)Co(NAnisole)](PF6)3 (3). All complexes were fully characterized, including single-crystal X-ray diffraction (SC-XRD) analyses, infrared (IR) vibrational, ultraviolet/visible (UV/vis) electronic absorption, multinuclear NMR, X-band electron paramagnetic resonance (EPR), electron nuclear double resonance (ENDOR), and high-energy-resolution fluorescence-detected X-ray absorption spectroscopy (HERFD XAS). Quantum chemical calculations provide additional insight into the electronic structures of all compounds. The dicationic CoIV imido complex 2 exhibits a doublet ground state with considerable imidyl character as a result of covalent Co-NAnisole bonding. At room temperature, 2 readily converts to a CoII amine complex involving intramolecular C-H bond amination. Electronically, tricationic complex 3 can be understood as a singlet nitrene bound to CoIII with significant CoIV imidyl radical character. Verifying the pronounced electrophilicity, nucleophiles such as H2O and tBuNH2 add to 3─analogous to the parent free nitrene─in the para position of the aromatic substituent, thus, clearly corroborating singlet nitrene-type reactivity.

Closed Synthetic Cycle for Nickel-Based Dihydrogen Formation.

Dihydrogen evolution was observed in a two-step protonation reaction starting from a Ni0 precursor with a tripodal N-heterocyclic carbene (NHC) ligand. Upon the first protonation, a NiII monohydride complex was formed, which was isolated and fully characterized. Subsequent protonation yields H2 via a transient intermediate (INT) and an isolable NiII acetonitrile complex. The latter can be reduced to regenerate its Ni0 precursor. The mechanism of H2 formation was investigated by using a deuterated acid and scrutinized by 1 H NMR spectroscopy and gas chromatography. Remarkably, the second protonation forms a rare nickel dihydrogen complex, which was detected and identified in solution and characterized by 1 H NMR spectroscopy. DFT-based computational analyses were employed to propose a reaction profile and a molecular structure of the Ni-H2 complex. Thus, a dihydrogen-evolving, closed-synthetic cycle is reported with a rare Ni-H2 species as a key intermediate.

Homoleptic Acetylacetonate (acac) and ß-Ketoiminate (acnac) Complexes of Uranium.

Transmetalation of potassium salts of differently substituted acetylacetonate (acac) and ß-ketoiminate (acnac) with [U(I)3(dioxane)1.5] and [U(I)4(dioxane)2] resulted in the formation of homoleptic, octahedral complexes [U(tBuacnacPh)3] (with tBuacnacPh = 2,2,6,6-tetramethyl-5-(phenylimino)heptan-3-onate) in the oxidation states +III and +IV and the homoleptic, square prismatic complexes [UIV(MeacnacPh)4] (with MeacnacPh = 4-(phenylimino)pentan-2-onate) and the homoleptic, square antiprismatic complexes [U(tBuacac)4] [with acac = 2,2,6,6-tetramethyl-3,5-heptanedionate (tBuacac), 2,2,6,6-tetramethyl,4-methyl-3,5-heptanedionate (tBuacMeac), and 2,2,6,6-tetramethyl-4-phenyl-3,5-heptanedionate (tBuacPhac)] in oxidation states +III, +IV, and +V. Oxidation of [UIII(tBuacnacPh)3] (1) with AgOTf yielded [UIV(tBuacnacPh)3][OTf] (2), which was fully characterized by single-crystal X-ray diffraction analysis, a combination of ultraviolet/visible/near-infrared, nuclear magnetic resonance, and infrared spectroscopies, and solid-state superconducting quantum interference device magnetization studies. Complexation of the sterically less encumbering ligand derivative MeacnacPh provided access to the tetravalent, square antiprismatic complex [UIV(MeacnacPh)4] (3). Cyclovoltammetric analysis of the square antiprismatic [UIV(tBuacac)4] (4), [UIV(tBuacMeac)4] (5), and [UIV(tBuacPhac)4] (6) revealed reversible anodic and cathodic waves, attributable to the U(III/IV) and U(IV/V) redox couples, both being chemically accessible, as tested in the case of 5. The corresponding U(III) and U(V) compounds, [K(2.2.2-cryptand)][UIII(tBuacMeac)4] (7) and [UV(tBuacMeac)4][SbF6] (8), were synthesized accordingly. Unfortunately, reduced 7 proved to be too reactive for isolation and could only be detected by electron paramagnetic resonance spectroscopy. Notably, electrochemical studies on homoleptic uranium(IV) complexes with differently derivatized (R) acRac ligands (R = H, Me, or Ph) feature large electrochemical windows of up to 2.91 V, measured between the uranium(III) and the uranium(V) species, in addition to high stability toward repeated potential scans.

Iron-Catalyzed Intermolecular C-H Amination Assisted by an Isolated Iron-Imido Radical Intermediate.

Here we report the use of a base metal complex [(tBu pyrpyrr2 )Fe(OEt2 )] (1-OEt2 ) (tBu pyrpyrr2 2- =3,5-tBu2 -bis(pyrrolyl)pyridine) as a catalyst for intermolecular amination of Csp3 -H bonds of 9,10-dihydroanthracene (2 a) using 2,4,6-trimethyl phenyl azide (3 a) as the nitrene source. The reaction is complete within one hour at 80 °C using as low as 2 mol % 1-OEt2 with control in selectivity for single C-H amination versus double C-H amination. Catalytic C-H amination reactions can be extended to other substrates such as cyclohexadiene and xanthene derivatives and can tolerate a variety of aryl azides having methyl groups in both ortho positions. Under stoichiometric conditions the imido radical species [(tBu pyrpyrr2 )Fe{=N(2,6-Me2 -4-tBu-C6 H2 )] (1-imido) can be isolated in 56 % yield, and spectroscopic, magnetometric, and computational studies confirmed it to be an S = 1 FeIV complex. Complex 1-imido reacts with 2 a to produce the ferrous aniline adduct [(tBu pyrpyrr2 )Fe{NH(2,6-Me2 -4-tBu-C6 H2 )(C14 H11 )}] (1-aniline) in 45 % yield. Lastly, it was found that complexes 1-imido and 1-aniline are both competent intermediates in catalytic intermolecular C-H amination.

Tale of Three Molecular Nitrides: Mononuclear Vanadium (V) and (IV) Nitrides As Well As a Mixed-Valence Trivanadium Nitride Having a V3N4 Double-Diamond Core.

Transmetallation of [VCl3(THF)3] and [TlTptBu,Me] afforded [(TptBu,Me)VCl2] (1, TptBu,Me = hydro-tris(3-tert-butyl-5-methylpyrazol-1-yl)borate), which was reduced with KC8 to form a C3v symmetric VII complex, [(TptBu,Me)VCl] (2). Complex 1 has a high-spin (S = 1) ground state and displays rhombic high-frequency and -field electron paramagnetic resonance (HFEPR) spectra, while complex 2 has an S = 3/2 4A2 ground state observable by conventional EPR spectroscopy. Complex 1 reacts with NaN3 to form the VV nitride-azide complex [(TptBu,Me)V≡N(N3)] (3). A likely VIII azide intermediate en route to 3, [(TptBu,Me)VCl(N3)] (4), was isolated by reacting 1 with N3SiMe3. Complex 4 is thermally stable but reacts with NaN3 to form 3, implying a bis-azide intermediate, [(TptBu,Me)V(N3)2] (A), leading to 3. Reduction of 3 with KC8 furnishes a trinuclear and mixed-valent nitride, [{(TptBu,Me)V}2(µ4-VN4)] (5), conforming to a Robin-Day class I description. Complex 5 features a central vanadium ion supported only by bridging nitride ligands. Contrary to 1, complex 2 reacts with NaN3 to produce an azide-bridged dimer, [{(TptBu,Me)V}2(1,3-µ2-N3)2] (6), with two antiferromagnetically coupled high-spin VII ions. Complex 5 could be independently produced along with [(κ2-TptBu,Me)2V] upon photolysis of 6 in arene solvents. The putative {VIV≡N} intermediate, [(TptBu,Me)V≡N] (B), was intercepted by photolyzing 6 in a coordinating solvent, such as tetrahydrofuran (THF), yielding [(TptBu,Me)V≡N(THF)] (B-THF). In arene solvents, B-THF expels THF to afford 5 and [(κ2-TptBu,Me)2V]. A more stable adduct (B-OPPh3) was prepared by reacting B-THF with OPPh3. These adducts of B are the first neutral and mononuclear VIV nitride complexes to be isolated.

Intense Photoinduced Intervalence Charge Transfer in High-Valent Iron Mixed Phenolate/Carbene Complexes.

We report high-valent iron complexes supported by N-heterocyclic carbene (NHC)-anchored, bis-phenolate pincer ligands that undergo ligand-to-metal charge transfer (LMCT) upon photoexcitation. The resulting excited states - with a lifetime in the picosecond range - feature a ligand-based, mixed-valence system and intense intervalence charge transfer bands in the near-infrared region. Upon oxidation of the complex, corresponding intervalence charge transfer absorptions are also observed in the ground state. We suggest that the spectroscopic hallmarks of such LMCT states provide useful tools to decipher excited-state decay mechanisms in high-valent NHC complexes. Our observations further indicate that NHC-anchored, bis-phenolate pincer ligands are not sufficiently strong donors to prevent the population of excited metal-centered states in high-valent iron complexes.