Ashley J. Wooles

Bis(phosphorus-stabilised)methanide and methandiide derivatives of group 1-5 and f-element metals

In the past 11 years bis(phosphorus-stabilised)methanides and methandiides have emerged as valuable ligands for metals across the periodic table. This Review, focussing on structurally characterised examples, covers the synthesis, bonding, and reaction chemistry of {CH(PR2NR′)2}− methanide and {C(PR...

Thorium-phosphorus triamidoamine complexes containing Th-P single- and multiple-bond interactions.

Despite the burgeoning field of uranium-ligand multiple bonds, analogous complexes involving other actinides remain scarce. For thorium, under ambient conditions only a few multiple bonds to carbon, nitrogen, oxygen, sulfur, selenium and tellurium are reported, and no multiple bonds to phosphorus are known, reflecting a general paucity of synthetic methodologies and also problems associated with stabilising these linkages at the large thorium ion. Here we report structurally authenticated examples of a parent thorium(IV)–phosphanide (Th–PH2), a terminal thorium(IV)–phosphinidene (Th=PH), a parent dithorium(IV)–phosphinidiide (Th–P(H)-Th) and a discrete actinide–phosphido complex under ambient conditions (Th=P=Th). Although thorium is traditionally considered to have dominant 6d-orbital contributions to its bonding, contrasting to majority 5f-orbital character for uranium, computational analyses suggests that the bonding of thorium can be more nuanced, in terms of 5f- versus 6d-orbital composition and also significant involvement of the 7s-orbital and how this affects the balance of 5f- versus 6d-orbital bonding character.

Isolation of Elusive HAsAsH in a Crystalline Diuranium(IV) Complex

The HAsAsH molecule has hitherto only been proposed tentatively as a short-lived species generated in electrochemical or microwave-plasma experiments. After two centuries of inconclusive or disproven claims of HAsAsH formation in the condensed phase, we report the isolation and structural authentication of HAsAsH in the diuranium(IV) complex [{U(TrenTIPS)}2(μ-η2:η2-As2H2)] (3, TrenTIPS=N(CH2CH2NSiPri3)3; Pri=CH(CH3)2). Complex 3 was prepared by deprotonation and oxidative homocoupling of an arsenide precursor. Characterization and computational data are consistent with back-bonding-type interactions from uranium to the HAsAsH π*-orbital. This experimentally confirms the theoretically predicted excellent π-acceptor character of HAsAsH, and is tantamount to full reduction to the diarsane-1,2-diide form.

Molecular and electronic structure of terminal and alkali metal-capped uranium(V) nitride complexes

Determining the electronic structure of actinide complexes is intrinsically challenging because inter-electronic repulsion, crystal field, and spin–orbit coupling effects can be of similar magnitude. Moreover, such efforts have been hampered by the lack of structurally analogous families of complexes to study. Here we report an improved method to U≡N triple bonds, and assemble a family of uranium(V) nitrides. Along with an isoelectronic oxo, we quantify the electronic structure of this 5f1 family by magnetometry, optical and electron paramagnetic resonance (EPR) spectroscopies and modelling. Thus, we define the relative importance of the spin–orbit and crystal field interactions, and explain the experimentally observed different ground states. We find optical absorption linewidths give a potential tool to identify spin–orbit coupled states, and show measurement of UV···UV super-exchange coupling in dimers by EPR. We show that observed slow magnetic relaxation occurs via two-phonon processes, with no obvious correlation to the crystal field.

Covalent Uranium Carbene Chemistry

After seminal reports of covalent uranium carbene U˭C complexes in the 1980s by Gilje, the area fell dormant for around 30 years. However, in the past five years, there has been a resurgence of interest in the area. Despite recent advances, the classification of these U˭C complexes as either methanediides, carbenes, or alkylidenes has remained a contentious issue. Herein, we review U˭C complexes reported to date, along with reactivity and computational studies, and conclude that although U˭C complexes sit midway on the continuum between rare-earth methanediides and Schrock-type alkylidenes, they can be justifiably described as carbenes. GRAPHICAL ABSTRACT

Triamidoamine Thorium-Arsenic Complexes with Parent Arsenide, Arsinidiide and Arsenido Structural Motifs

Despite a major expansion of uranium–ligand multiple bond chemistry in recent years, analogous complexes involving other actinides (An) remain scarce. For thorium, under ambient conditions only a few multiple bonds to carbon, nitrogen, phosphorus and chalcogenides are reported, and none to arsenic are known; indeed only two complexes with thorium–arsenic single bonds have been structurally authenticated, reflecting the challenges of stabilizing polar linkages at the large thorium ion. Here, we report thorium parent–arsenide (ThAsH2), –arsinidiides (ThAs(H)K and ThAs(H)Th) and arsenido (ThAsTh) linkages stabilized by a bulky triamidoamine ligand. The ThAs(H)K and ThAsTh linkages exhibit polarized-covalent thorium–arsenic multiple bonding interactions, hitherto restricted to cryogenic matrix isolation experiments, and the AnAs(H)An and AnAsAn linkages reported here have no precedent in f-block chemistry. 7s, 6d and 5f orbital contributions to the Th–As bonds are suggested by quantum chemical calculations, and their compositions unexpectedly appear to be tensioned differently compared to phosphorus congeners.

Crystalline Diuranium-Phosphinidiide and -μ-Phosphido Complexes with Symmetric and Asymmetric UPU Cores

Abstract Reaction of [U(TrenTIPS)(PH2)] (1, TrenTIPS=N(CH2CH2NSiPri 3)3) with C6H5CH2K and [U(TrenTIPS)(THF)][BPh4] (2) afforded a rare diuranium parent phosphinidiide complex [{U(TrenTIPS)}2(μ‐PH)] (3). Treatment of 3 with C6H5CH2K and two equivalents of benzo‐15‐crown‐5 ether (B15C5) gave the diuranium μ‐phosphido complex [{U(TrenTIPS)}2(μ‐P)][K(B15C5)2] (4). Alternatively, reaction of [U(TrenTIPS)(PH)][Na(12C4)2] (5, 12C4=12‐crown‐4 ether) with [U{N(CH2CH2NSiMe2But)2CH2CH2NSi(Me)(CH2)(But)}] (6) produced the diuranium μ‐phosphido complex [{U(TrenTIPS)}(μ‐P){U(TrenDMBS)}][Na(12C4)2] [7, TrenDMBS=N(CH2CH2NSiMe2But)3]. Compounds 4 and 7 are unprecedented examples of uranium phosphido complexes outside of matrix isolation studies, and they rapidly decompose in solution underscoring the paucity of uranium phosphido complexes. Interestingly, 4 and 7 feature symmetric and asymmetric UPU cores, respectively, reflecting their differing steric profiles.

Catalytic Dinitrogen Reduction to Ammonia at a Triamidoamine–Titanium Complex

Abstract Catalytic reduction of N2 to NH3 by a Ti complex has been achieved, thus now adding an early d‐block metal to the small group of mid‐ and late‐d‐block metals (Mo, Fe, Ru, Os, Co) that catalytically produce NH3 by N2 reduction and protonolysis under homogeneous, abiological conditions. Reduction of [TiIV(TrenTMS)X] (X=Cl, 1A; I, 1B; TrenTMS=N(CH2CH2NSiMe3)3) with KC8 affords [TiIII(TrenTMS)] (2). Addition of N2 affords [{(TrenTMS)TiIII}2(μ‐η1:η1‐N2)] (3); further reduction with KC8 gives [{(TrenTMS)TiIV}2(μ‐η1:η1:η2:η2‐N2K2)] (4). Addition of benzo‐15‐crown‐5 ether (B15C5) to 4 affords [{(TrenTMS)TiIV}2(μ‐η1:η1‐N2)][K(B15C5)2]2 (5). Complexes 3–5 treated under N2 with KC8 and [R3PH][I], (the weakest H+ source yet used in N2 reduction) produce up to 18 equiv of NH3 with only trace N2H4. When only acid is present, N2H4 is the dominant product, suggesting successive protonation produces [{(TrenTMS)TiIV}2(μ‐η1:η1‐N2H4)][I]2, and that extruded N2H4 reacts further with [R3PH][I]/KC8 to form NH3.

Terminal Parent Phosphanide and Phosphinidene Complexes of Zirconium(IV)

Abstract The reaction of [Zr(TrenDMBS)(Cl)] [Zr1; TrenDMBS=N(CH2CH2NSiMe2But)3] with NaPH2 gave the terminal parent phosphanide complex [Zr(TrenDMBS)(PH2)] [Zr2; Zr−P=2.690(2) Å]. Treatment of Zr2 with one equivalent of KCH2C6H5 and two equivalents of benzo‐15‐crown‐5 ether (B15C5) afforded an unprecedented example (outside of matrix isolation) of a structurally authenticated transition‐metal terminal parent phosphinidene complex [Zr(TrenDMBS)(PH)][K(B15C5)2] [Zr3; Zr=P=2.472(2) Å]. DFT calculations reveal a polarized‐covalent Zr=P double bond, with a Mayer bond order of 1.48, and together with IR spectroscopic data also suggest an agostic‐type Zr⋅⋅⋅HP interaction [∡ZrPH=66.7°] which is unexpectedly similar to that found in cryogenic, spectroscopically observed phosphinidene species. Surprisingly, computational data suggest that the Zr=P linkage is similarly polarized, and thus as covalent, as essentially isostructural U=P and Th=P analogues.

Actinide-Pnictide (An-Pn) Bonds Spanning -Non-Metal, -Metalloid, and - Metal Combinations (An = U, Th; Pn = P, As, Sb, Bi)

Abstract The synthesis and characterisation is presented of the compounds [An(TrenDMBS){Pn(SiMe3)2}] and [An(TrenTIPS){Pn(SiMe3)2}] [TrenDMBS=N(CH2CH2NSiMe2But)3, An=U, Pn=P, As, Sb, Bi; An=Th, Pn=P, As; TrenTIPS=N(CH2CH2NSiPri 3)3, An=U, Pn=P, As, Sb; An=Th, Pn=P, As, Sb]. The U−Sb and Th−Sb moieties are unprecedented examples of any kind of An−Sb molecular bond, and the U−Bi bond is the first two‐centre‐two‐electron (2c–2e) one. The Th−Bi combination was too unstable to isolate, underscoring the fragility of these linkages. However, the U−Bi complex is the heaviest 2c–2e pairing of two elements involving an actinide on a macroscopic scale under ambient conditions, and this is exceeded only by An−An pairings prepared under cryogenic matrix isolation conditions. Thermolysis and photolysis experiments suggest that the U−Pn bonds degrade by homolytic bond cleavage, whereas the more redox‐robust thorium compounds engage in an acid–base/dehydrocoupling route.