Siloxide tripodal ligands as a scaffold for stabilizing lanthanides in the +4 oxidation state.

Synthetic strategies to isolate molecular complexes of lanthanides, other than cerium, in the +4 oxidation state remain elusive, with only four complexes of Tb(iv) isolated so far. Herein, we present a new approach for the stabilization of Tb(iv) using a siloxide tripodal trianionic ligand, which allows the control of unwanted ligand rearrangements, while tuning the Ln(iii)/Ln(iv) redox-couple. The Ln(iii) complexes, [LnIII((OSiPh2Ar)3-arene)(THF)3] (1-LnPh) and [K(toluene){LnIII((OSiPh2Ar)3-arene)(OSiPh3)}] (2-LnPh) (Ln = Ce, Tb, Pr), of the (HOSiPh2Ar)3-arene ligand were prepared. The redox properties of these complexes were compared to those of the Ln(iii) analogue complexes, [LnIII((OSi(OtBu)2Ar)3-arene)(THF)] (1-LnOtBu) and [K(THF)6][LnIII((OSi(OtBu)2Ar)3-arene)(OSiPh3)] (2-LnOtBu) (Ln = Ce, Tb), of the less electron-donating siloxide trianionic ligand, (HOSi(OtBu)2Ar)3-arene. The cyclic voltammetry studies showed a cathodic shift in the oxidation potential for the cerium and terbium complexes of the more electron-donating phenyl substituted scaffold (1-LnPh) compared to those of the tert-butoxy (1-LnOtBu) ligand. Furthermore, the addition of the -OSiPh3 ligand further shifts the potential cathodically, making the Ln(iv) ion even more accessible. Notably, the Ce(iv) complexes, [CeIV((OSi(OtBu)2Ar)3-arene)(OSiPh3)] (3-CeOtBu) and [CeIV((OSiPh2Ar)3-arene)(OSiPh3)(THF)2] (3-CePh), were prepared by chemical oxidation of the Ce(iii) analogues. Chemical oxidation of the Tb(iii) and Pr(iii) complexes (2-LnPh) was also possible, in which the Tb(iv) complex, [TbIV((OSiPh2Ar)3-arene)(OSiPh3)(MeCN)2] (3-TbPh), was isolated and crystallographically characterized, yielding the first example of a Tb(iv) supported by a polydentate ligand. The versatility and robustness of these siloxide arene-anchored platforms will allow further development in the isolation of more oxidizing Ln(iv) ions, widening the breadth of high-valent Ln chemistry.

Iron promoted end-on dinitrogen-bridging in heterobimetallic complexes of uranium and lanthanides.

End-on binding of dinitrogen to low valent metal centres is common in transition metal chemistry but remains extremely rare in f-elements chemistry. In particular, heterobimetallic end-on N2 bridged complexes of lanthanides are unprecedented despite their potential relevance in catalytic reduction of dinitrogen. Here we report the synthesis and characterization of a series of N2 bridged heterobimetallic complexes of U(iii), Ln(iii) and Ln(ii) which were prepared by reacting the Fe dinitrogen complex [Fe(depe)2(N2)] (depe = 1,2-bis(diethylphosphino)-ethane), complex A with [MIII{N(SiMe3)2}3] (M = U, Ce, Sm, Dy, Tm) and [LnII{N(SiMe3)2}2], (Ln = Sm, Yb). Despite the lack of reactivity of the U(iii), Ln(iii) and Ln(ii) amide complexes with dinitrogen, the end-on dinitrogen bridged heterobimetallic complexes [{Fe(depe)2}(µ-η1:η1-N2)(M{N(SiMe3)2}3)], 1-M (M = U(iii), Ce(iii), Sm(iii), Dy(iii) and Tm(iii)), [{Fe(depe)2}(µ-η1:η1-N2)(Ln{N(SiMe3)2}2)], 1*-Ln (Ln = Sm(ii), Yb(ii)) and [{Fe(depe)2(µ-η1:η1-N2)}2{SmII{N(SiMe3)2}2}], 3 could be prepared. The synthetic method used here allowed to isolate unprecedented end-on bridging N2 complexes of divalent lanthanides which provide relevant structural models for the species involved in the catalytic reduction of dinitrogen by Fe/Sm(ii) systems. Computational studies showed an essentially electrostatic interaction of the end-on bridging N2 with both Ln(iii) and Ln(ii) complexes with the degree of N2 activation correlating with their Lewis acidity. In contrast, a back-bonding covalent contribution to the U(iii)-N2Fe bond was identified by computational studies. Computational studies also suggest that end-on binding of N2 to U(iii) and Ln(ii) complexes is favoured for the iron-bound N2 compared to free N2 due to the higher N2 polarization.

Molecular imine cages with π-basic Au3(pyrazolate) faces.

One tetrahedral and two trigonal prismatic cages with π-basic Au3(pyrazolate)3 faces were obtained by connection of pre-formed gold complexes via dynamic covalent imine chemistry. The parallel arrangement of the Au3(pyrazolate)3 complexes in the prismatic cages augments the interaction with π-acids, as demonstrated by the encapsulation of polyhalogenated aromatic compounds. The tetrahedral cage was found to act as a potent receptor for fullerenes. The structures of the three cages, as well as the structures of adducts with C60 and C70, could be established by X-ray crystallography.

Accessing a Highly Reducing Uranium(III) Complex through Cyclometalation.

U(IV) cyclometalated complexes have shown rich reactivity, but their low oxidation state analogues still remain rare. Herein, we report the isolation of [K(2.2.2-cryptand)][UIII{N(SiMe3)2}2(κ2-C,N-CH2SiMe2NSiMe3)], 1, from the reduction of [UIII{N(SiMe)2}3] with KC8 and 2.2.2-cryptand at room temperature. Cyclic voltammetry studies demonstrate that 1 has a reduction potential similar to that of the previously reported [K(2.2.2-cryptand)][UII{N(SiMe)2}3] (Epc = -2.6 V versus Fc+/0 and Epc = -2.8 V versus Fc+/0, respectively). Complex 1, indeed, shows similar reducing abilities upon reactions with 4,4'-bipyridine, 2,2'-bipyridine, and 1-azidoadamantane. Interestingly, 1 was also found to be the first example of a mononuclear U(III) complex that is capable of reducing pyridine. In addition, it is shown that a wide variety of substrates can be inserted into the U-C bond, forming new U(III) metallacycles. These results highlight that cyclometalated U(III) complexes can serve as versatile precursors for a broad range of reactivity and for assembling a variety of novel chemical architectures.

Two-Electron Redox Reactivity of Thorium Supported by Redox-Active Tripodal Frameworks.

The high stability of the + IVoxidation state limits thorium redox reactivity. Here we report the synthesis and the redox reactivity of two Th(IV) complexes supported by the arene-tethered tris(siloxide) tripodal ligands [(KOSiR2 Ar)3 -arene)]. The two-electron reduction of these Th(IV) complexes generates the doubly reduced [KTh((OSi(Ot Bu)2 Ar)3 -arene)(THF)2 ] (2OtBu ) and [K(2.2.2-cryptand)][Th((OSiPh2 Ar)3 -arene)(THF)2 ](2Ph -crypt) where the formal oxidation state of Th is +II. Structural and computational studies indicate that the reduction occurred at the arene anchor of the ligand. The robust tripodal frameworks store in the arene anchor two electrons that become available at the metal center for the two-electron reduction of a broad range of substrates (N2 O, COT, CHT, Ph2 N2 , Ph3 PS and O2 ) while retaining the ligand framework. This work shows that arene-tethered tris(siloxide) tripodal ligands allow implementation of two-electron redox chemistry at the thorium center while retaining the ligand framework unchanged.

A trinuclear metallasilsesquioxane of uranium(III).

The silsesquioxane ligand (iBu)7Si7O9(OH)3 (iBuPOSSH3) is revealed as an attractive system for the assembly of robust polynuclear complexes of uranium(III) and allowed the isolation of the first example of a trinuclear U(III) complex ([U3(iBuPOSS)3]) that exhibits magnetic communication and promotes dinitrogen reduction in the presence of reducing agent.

Multimetallic Uranium Nitride Cubane Clusters from Dinitrogen Cleavage.

Dinitrogen cleavage provides an attractive but poorly studied route to the assembly of multimetallic nitride clusters. Here, we show that the monoelectron reduction of the dinitrogen complex [{U(OC6H2-But3-2,4,6)3}2(µ-η2:η2-N2)], 1, allows us to generate, for the first time, a uranium complex presenting a rare triply reduced N2 moiety ((µ-η2:η2-N2)•3-). Importantly, the bound dinitrogen can be further reduced, affording the U4N4 cubane cluster, 3, and the U6N6 edge-shared cubane cluster, 4, thus showing that (N2)•3- can be an intermediate in nitride formation. The tetranitride cluster showed high reactivity with electrophiles, yielding ammonia quantitatively upon acid addition and promoting CO cleavage to yield quantitative conversion of nitride into cyanide. These results show that dinitrogen reduction provides a versatile route for the assembly of large highly reactive nitride clusters, with U6N6 providing the first example of a molecular nitride of any metal formed from a complete cleavage of three N2 molecules.

Dinitrogen cleavage by a dinuclear uranium(iii) complex.

Understanding the role of multimetallic cooperativity and of alkali ion-binding in the second coordination sphere is important for the design of complexes that can promote dinitrogen (N2) cleavage and functionalization. Herein, we compare the reaction products and mechanism of N2 reduction of the previously reported K2-bound dinuclear uranium(iii) complex, [K2{[UIII(OSi(OtBu)3)3]2(µ-O)}], B, with those of the analogous dinuclear uranium(iii) complexes, [K(2.2.2-cryptand)][K{UIII(OSi(OtBu)3)3}2(µ-O)], 1, and [K(2.2.2-cryptand)]2[{UIII(OSi(OtBu)3)3}2(µ-O)], 2, where one or two K+ ions have been removed from the second coordination sphere by addition of 2.2.2-cryptand. In this study, we found that the complete removal of the K+ ions from the inner coordination sphere leads to an enhanced reducing ability, as confirmed by cyclic voltammetry studies, of the resulting complex 2, and yields two new species upon N2 addition, namely the U(iii)/U(iv) complex, [K(2.2.2-cryptand)][{UIII(OSi(OtBu)3)3}(µ-O){UIV(OSi(OtBu)3)3}], 3, and the N2 cleavage product, the bis-nitride, terminal-oxo complex, [K(2.2.2-cryptand)]2[{UV(OSi(OtBu)3)3}(µ-N)2{UVI(OSi(OtBu)3)2(κ-O)}], 4. We propose that the formation of these two products involves a tetranuclear uranium-N2 intermediate that can only form in the absence of coordinated alkali ions, resulting in a six-electron transfer and cleavage of N2, demonstrating the possibility of a three-electron transfer from U(iii) to N2. These results give an insight into the relationship between alkali ion binding modes, multimetallic cooperativity and reactivity, and demonstrate how these parameters can be tuned to cleave and functionalize N2.

Multielectron Redox Chemistry of Uranium by Accessing the +II Oxidation State and Enabling Reduction to a U(I) Synthon.

The synthesis of molecular uranium complexes in oxidation states lower than +3 remains a challenge despite the interest for their multielectron transfer reactivity and electronic structures. Herein, we report the one- and two-electron reduction of a U(III) complex supported by an arene-tethered tris(siloxide) tripodal ligand leading to the mono-reduced complexes, [K(THF)U((OSi(OtBu)2Ar)3-arene)(THF)] (2) and [K(2.2.2-cryptand)][U((OSi(OtBu)2Ar)3-arene)(THF)] (2-crypt), and to the di-reduced U(I) synthons, [K2(THF)3U((OSi(OtBu)2Ar)3-arene)]∞ (3) and [(K(2.2.2-cryptand))]2[U((OSi(OtBu)2Ar)3-arene)] (3-crypt). EPR and UV/vis/NIR spectroscopies, magnetic, cyclic voltammetry, and computational studies provide strong evidence that complex 2-crypt is best described as a U(II), where the U(II) is stabilized by δ-bonding interactions between the arene anchor and the uranium frontier orbitals, whereas complexes 3 and 3-crypt are best described as having a U(III) ion supported by the di-reduced arene anchor. Three quasi-reversible redox waves at E1/2 = -3.27, -2.45, and -1.71 V were identified by cyclic voltammetry studies and were assigned to the U(IV)/U(III), U(III)/U(II), and U(II)/U(III)-(arene)2- redox couples. The ability of complexes 2 and 3 in transferring two- and three-electrons, respectively, to oxidizing substrates was confirmed by the reaction of 2 with azobenzene (PhNNPh), leading to the U(IV) complex, [K(Et2O)U((OSi(OtBu)2Ar)3-arene)(PhNNPh)(THF)] (4), and of complex 3 with cycloheptatriene, yielding the U(IV) complex, [(K(Et2O)2)U((OSi(OtBu)2Ar)3-arene)(η7-C7H7)]∞ (6). These results demonstrate that the arene-tethered tris(siloxide) tripodal ligand provides an excellent platform for accessing low-valent uranium chemistry while implementing multielectron transfer pathways as shown by the reactivity of complex 3, which provides the third example of a U(I) synthon.

Electro- and photochemical H2 generation by Co(ii) polypyridyl-based catalysts bearing ortho-substituted pyridines.

Cobalt(ii) complexes featuring hexadentate amino-pyridyl ligands have been recently discovered as highly active catalysts for the Hydrogen Evolution Reaction (HER), whose high performance arises from the possibility of assisting proton transfer processes via intramolecular routes involving detached pyridine units. With the aim of gaining insights into such catalytic routes, three new proton reduction catalysts based on amino-polypyridyl ligands are reported, focusing on substitution of the pyridine ortho-position. Specifically, a carboxylate (C2) and two hydroxyl substituted pyridyl moieties (C3, C4) are introduced with the aim of promoting intramolecular proton transfer which possibly enhances the efficiency of the catalysts. Foot-of-the-wave and catalytic Tafel plot analyses have been utilized to benchmark the catalytic performances under electrochemical conditions in acetonitrile using trifluoroacetic acid as the proton source. In this respect, the cobalt complex C3 turns out to be the fastest catalyst in the series, with a maximum turnover frequency (TOF) of 1.6 (±0.5) × 105 s-1, but at the expense of large overpotentials. Mechanistic investigations by means of Density Functional Theory (DFT) suggest a typical ECEC mechanism (i.e. a sequence of reduction - E - and protonation - C - events) for all the catalysts, as previously envisioned for the parent unsubstituted complex C1. Interestingly, in the case of complex C2, the catalytic route is triggered by initial protonation of the carboxylate group resulting in a less common (C)ECEC mechanism. The pivotal role of the hexadentate chelating ligand in providing internal proton relays to assist hydrogen elimination is further confirmed within this novel class of molecular catalysts, thus highlighting the relevance of a flexible polypyridine ligand in the design of efficient cobalt complexes for the HER. Photochemical studies in aqueous solution using [Ru(bpy)3]2+ (where bpy = 2,2'-bipyridine) as the sensitizer and ascorbate as the sacrificial electron donor support the superior performance of C3.

MOF-Based Solid-State Proton Conductors Obtained by Intertwining Protic Ionic Liquid Polymers with MIL-101.

Solid-state proton conductors based on the use of metal-organic framework (MOF) materials as proton exchange membranes are being investigated as alternatives to the current state of the art. This study reports a new family of proton conductors based on MIL-101 and protic ionic liquid polymers (PILPs) containing different anions. By first installing protic ionic liquid (PIL) monomers inside the hierarchical pores of a highly stable MOF, MIL-101, then carrying out polymerization in situ, a series of PILP@MIL-101 composites was synthesized. The resulting PILP@MIL-101 composites not only maintain the nanoporous cavities and water stability of MIL-101, but the intertwined PILPs provide a number of opportunities for much-improved proton transport compared to MIL-101. The PILP@MIL-101 composite with HSO4 - anions shows superprotonic conductivity (6.3 × 10-2  S cm-1 ) at 85 °C and 98% relative humidity. The mechanism of proton conduction is proposed. In addition, the structures of the PIL monomers were determined by single crystal X-ray analysis, which reveals many strong hydrogen bonding interactions with O/NH···O distances below 2.6 Å.

Synthesis and Reactivity of an Anionic Diazoolefin.

Bent (hetero)allenes such as carbodicarbenes and carbodiphosphoranes can act as neutral C-donor ligands, and diverse applications in coordination chemistry have been reported. N-Heterocyclic diazoolefins are heterocumulenes, which can function in a similar fashion as L-type ligands. Herein, we describe the synthesis and the reactivity of an anionic diazoolefin. This compound displays distinct reactivity compared to neutral diazoolefins, as evidenced by the preparation of diazo compounds via protonation, alkylation, or silylation. The anionic diazoolefin can be employed as an ambidentate, X-type ligand in salt metathesis reactions with metal halide complexes. Extrusion of dinitrogen was observed in a reaction with PCl(NiPr2 )2 , resulting in a stable phosphinocarbene.

Isolation and redox reactivity of cerium complexes in four redox states.

The chemistry of lanthanides is limited to one electron transfer reactions due to the difficulty of accessing multiple oxidation states. Here we report that a redox-active ligand combining three siloxides with an arene ring in a tripodal ligand can stabilize cerium complexes in four different redox states and can promote multielectron redox reactivity in cerium complexes. Ce(iii) and Ce(iv) complexes [(LO3)Ce(THF)] (1) and [(LO3)CeCl] (2) (LO3 = 1,3,5-(2-OSi(OtBu)2C6H4)3C6H3) were synthesized and fully characterized. Remarkably the one-electron reduction and the unprecedented two-electron reduction of the tripodal Ce(iii) complex are easily achieved to yield reduced complexes [K(2.2.2-cryptand)][(LO3)Ce(THF)] (3) and [K2{(LO3)Ce(Et2O)3}] (5) that are formally "Ce(ii)" and "Ce(i)" analogues. Structural analysis, UV and EPR spectroscopy and computational studies indicate that in 3 the cerium oxidation state is in between +II and +III with a partially reduced arene. In 5 the arene is doubly reduced, but the removal of potassium results in a redistribution of electrons on the metal. The electrons in both 3 and 5 are stored onto δ-bonds allowing the reduced complexes to be described as masked "Ce(ii)" and "Ce(i)". Preliminary reactivity studies show that these complexes act as masked Ce(ii) and Ce(i) in redox reactions with oxidizing substrates such as Ag+, CO2, I2 and S8 effecting both one- and two-electron transfers that are not accessible in classical cerium chemistry.

Uranium(IV) and Thorium(IV) Coordination Polymers Based on Tritopic Carboxylic Acids.

Nine new coordination polymers based on U(IV) and Th(IV) were synthesized solvothermally utilizing four different trianionic carboxylates (H3BHTC = biphenyl-3,4',5-tricarboxylic acid, H3NTB = 4,4',4″-nitrilotribenzoic acid, H3BTB = 4,4',4″-benzene-1,3,5-triyl-tris(benzoic acid), H3BTE = 4,4',4″-(1,3,5-benzenetriyltri-2,1-ethynediyl)trisbenzoic acid). The influence of the ligand architecture, the pH, the stoichiometry, the nature of the metal, and the concentration on the structure and dimensionality of the final actinide assembly is discussed. The H3BHTC ligand allowed the synthesis of a cationic three-dimensional (3D) framework [U(BHTC)(DMF)3]I (1), which is the first example of a cationic U(IV) polymer. The H3NTB ligand yielded the 3D neutral polymer [U3(NTB)4] (2) or the two-dimensional (2D) cationic polymer [U(NTB)(NMP)3]I (3), depending on the solvent. When conditions leading to (2) were used with a Th(IV) precursor, the 2D neutral polymer [Th(NTB)(DMF)3Cl] (4) was obtained. The ligand H3BTB allowed the synthesis of two 3D cationic networks [U(BTB)(DMF)2]I (5) and [U(BTB)(DMF)3]I (7) or the neutral 3D analogue [U3(BTB)4] (6), depending on the precursor's oxidation state and the acidity of the reaction mixture. The ligand H3BTE allowed the synthesis of the anionic 3D [(CH3)2NH2][U2(BTE)3] (8) framework featuring large accessible pores, and under the same conditions, an isostructural Th(IV) was also obtained [(CH3)2NH2][Th2(BTE)3] (8-Th). All isolated coordination polymers were characterized by single-crystal X-ray diffraction (SCXRD). The Langmuir surface areas of the U(IV) polymers (2), (7), and (8) increased from 140 to 310 m2/g owing to the increasing size of the linker, with polymer (8) showing a value that is comparable to the highest surface area reported to date. The effect of the postsynthetic solvent substitution was also studied, revealing a crystal-to-crystal transformation of the cationic framework (7) to the neutral framework [U(BTB)(THF)I] (7c).

Retarding solid-state reactions enable efficient and stable all-inorganic perovskite solar cells and modules.

All-inorganic CsPbI3 perovskite solar cells (PSCs) with efficiencies exceeding 20% are ideal candidates for application in large-scale tandem solar cells. However, there are still two major obstacles hindering their scale-up: (i) the inhomogeneous solid-state synthesis process and (ii) the inferior stability of the photoactive CsPbI3 black phase. Here, we have used a thermally stable ionic liquid, bis(triphenylphosphine)iminium bis(trifluoromethylsulfonyl)imide ([PPN][TFSI]), to retard the high-temperature solid-state reaction between Cs4PbI6 and DMAPbI3 [dimethylammonium (DMA)], which enables the preparation of high-quality and large-area CsPbI3 films in the air. Because of the strong Pb-O contacts, [PPN][TFSI] increases the formation energy of superficial vacancies and prevents the undesired phase degradation of CsPbI3. The resulting PSCs attained a power conversion efficiency (PCE) of 20.64% (certified 19.69%) with long-term operational stability over 1000 hours. A record efficiency of 16.89% for an all-inorganic perovskite solar module was achieved, with an active area of 28.17 cm2.

Construction of Pd-based coordination cages with three geometrically distinct ligands.

Three different dipyridyl ligands were combined with [Pd(CH3CN)4](BF4)2 to give mixtures of homo- and/or heteroleptic coordination cages. The three ligands were chosen so that one ligand shows a parallel orientation of the coordinate vectors, the second ligand a bent angle of 60°, and the third ligand a bent angle of 120°. We have identified ligand mixtures that give rise to integrative self-sorting, and we have characterized a heterotrileptic [Pd4L2L'2L''4]8+ cage by single crystal X-ray crystallography. The structural flexibility of ligands with alkynyl spacers was found to be of importance for the formation of heteroleptic complexes.

A Route to Stabilize Uranium(II) and Uranium(I) Synthons in Multimetallic Complexes.

Herein, we report the redox reactivity of a multimetallic uranium complex supported by triphenylsiloxide (-OSiPh3 ) ligands, where we show that low valent synthons can be stabilized via an unprecedented mechanism involving intramolecular ligand migration. The two- and three-electron reduction of the oxo-bridged diuranium(IV) complex [{(Ph3 SiO)3 (DME)U}2 (µ-O)], 4, yields the formal "UII /UIV ", 5, and "UI /UIV ", 6, complexes via ligand migration and formation of uranium-arene δ-bond interactions. Remarkably, complex 5 effects the two-electron reductive coupling of pyridine affording complex 7, which demonstrates that the electron-transfer is accompanied by ligand migration, restoring the original ligand arrangement found in 4. This work provides a new method for controlling the redox reactivity in molecular complexes of unstable, low-valent metal centers, and can lead to the further development of f-elements redox reactivity.

Head-to-Tail Dimerization of N-Heterocyclic Diazoolefins.

The head-to-tail dimerization of N-heterocyclic diazoolefins is described. The products of these formal (3+3) cycloaddition reactions are strongly reducing quinoidal tetrazines. Oxidation of the tetrazines occurs in a stepwise fashion, and we were able to isolate a stable radical cation and diamagnetic dications. The latter are also accessible by oxidative dimerization of diazoolefins.

Copper Complexes with Diazoolefin Ligands and their Photochemical Conversion into Alkenylidene Complexes.

Homometallic copper complexes with alkenylidene ligands are discussed as intermediates in catalysis but the isolation of such complexes has remained elusive. Herein, we report the structural characterization of copper complexes with bridging and terminal alkenylidene ligands. The compounds were obtained by irradiation of CuI complexes with N-heterocyclic diazoolefin ligands. The complex with a terminal alkenylidene ligand required isolation in a crystalline matrix, and its structural characterization was enabled by in crystallo photolysis at low temperature.

Bonding and Reactivity in Terminal versus Bridging Arenide Complexes of Thorium Acting as ThII Synthons.

Thorium redox chemistry is extremely scarce due to the high stability of ThIV . Here we report two unique examples of thorium arenide complexes prepared by reduction of a ThIV -siloxide complex in presence of naphthalene, the mononuclear arenide complex [K(OSi(Ot Bu)3 )3 Th(η6 -C10 H8 )] (1) and the inverse-sandwich complex [K(OSi(Ot Bu)3 )3 Th]2 (µ-η6 ,η6 -C10 H8 )] (2). The electrons stored in these complexes allow the reduction of a broad range of substrates (N2 O, AdN3 , CO2 , HBBN). Higher reactivity was found for the complex 1 which reacts with the diazoolefin IDipp=CN2 to yield the unexpected ThIV amidoalkynyl complex 5 via a terminal N-heterocyclic vinylidene intermediate. This work showed that arenides can act as convenient redox-active ligands for implementing thorium-ligand cooperative multielectron transfer and that the reactivity can be tuned by the arenide binding mode.