Nikolas Kaltsoyannis

A Stable Two-Coordinate Acyclic Silylene

Simple two-coordinate acyclic silylenes, SiR(2), have hitherto been identified only as transient intermediates or thermally labile species. By making use of the strong σ-donor properties and high steric loading of the B(NDippCH)(2) substituent (Dipp = 2,6-(i)Pr(2)C(6)H(3)), an isolable monomeric species, Si{B(NDippCH)(2)}{N(SiMe(3))Dipp}, can be synthesized which is stable in the solid state up to 130 °C. This silylene species undergoes facile oxidative addition reactions with dihydrogen (at sub-ambient temperatures) and with alkyl C-H bonds, consistent with a low singlet-triplet gap (103.9 kJ mol(-1)), thus demonstrating fundamental modes of reactivity more characteristic of transition metal systems.

Does Covalency Increase or Decrease across the Actinide Series? Implications for Minor Actinide Partitioning

A covalent chemical bond carries the connotation of overlap of atomic orbitals between bonded atoms, leading to a buildup of the electron density in the internuclear region. Stabilization of the valence 5f orbitals as the actinide series is crossed leads, in compounds of the minor actinides americium and curium, to their becoming approximately degenerate with the highest occupied ligand levels and hence to the unusual situation in which the resultant valence molecular orbitals have significant contributions from both actinide and the ligand yet in which there is little atomic orbital overlap. In such cases, the traditional quantum-chemical tools for assessing the covalency, e.g., population analysis and spin densities, predict significant metal-ligand covalency, although whether this orbital mixing is really covalency in the generally accepted chemical view is an interesting question. This review discusses our recent analyses of the bonding in AnCp3 and AnCp4 (An = Th-Cm; Cp = η(5)-C5H5) using both the traditional tools and also topological analysis of the electron density via the quantum theory of atoms-in-molecules. I will show that the two approaches yield rather different conclusions and suggest that care must be taken when using quantum chemistry to assess metal-ligand covalency in this part of the periodic table. The implications of this work for minor actinide partitioning from nuclear wastes are discussed; minor actinide extractant ligands based on nitrogen donors have received much attention in recent years, as have comparisons of the extent of covalency in actinide-nitrogen bonding with that in analogous lanthanide systems via quantum-chemical studies employing the traditional tools for assessing the covalency.

Recent developments in computational actinide chemistry

This review describes recent computational investigations into the electronic and geometric structures of molecular actinide compounds. Following brief introductions to (i) the effects of relativity in chemistry and (ii) ab initio and density functional quantum chemical methods, four areas of contemporary research are discussed. These are pi backbonding in uranium complexes, the geometric structures of bis benzene actinide compounds, the valence electronic structure of the uranyl ion, and the inverse trans influence in pseudo-octahedral [AnOX5]n-. Comparisons are made with experimental studies, and similarities and differences between d- and f-block chemistry are highlighted.

Small Molecule Activation by Uranium Tris(aryloxides): Experimental and Computational Studies of Binding of N-2, Coupling of CO, and Deoxygenation Insertion of CO2 under Ambient Conditions

Previously unanticipated dinitrogen activation is exhibited by the well-known uranium tris(aryloxide) U(ODtbp)(3), U(OC(6)H(3)-Bu(t)(2)-2,6)(3), and the tri-tert-butyl analogue U(OTtbp)(3), U(OC(6)H(2)-Bu(t)(3)-2,4,6)(3), in the form of bridging, side-on dinitrogen complexes [U(OAr)(3)](2)(μ-η(2):η(2)-N(2)), for which the tri-tert-butyl N(2) complex is the most robust U(2)(N(2)) complex isolated to date. Attempted reduction of the tris(aryloxide) complex under N(2) gave only the potassium salt of the uranium(III) tetra(aryloxide) anion, K[U(OAr)(4)], as a result of ligand redistribution. The solid-state structure is a polymeric chain formed by each potassium cation bridging two arenes of adjacent anions in an η(6) fashion. The same uranium tris(aryloxides) were also found to couple carbon monoxide under ambient conditions to give exclusively the ynediolate [OCCO](2-) dianion in [U(OAr)(3)](2)(μ-η(1):η(1)-C(2)O(2)), in direct analogy with the reductive coupling recently shown to afford [U{N(SiMe(3))(2)}(3)](2)(μ-η(1):η(1)-C(2)O(2)). The related U(III) complexes U{N(SiPhMe(2))(2)}(3) and U{CH(SiMe(3))(2)}(3) however do not show CO coupling chemistry in our hands. Of the aryloxide complexes, only the U(OC(6)H(2)-Bu(t)(3)-2,4,6)(3) reacts with CO(2) to give an insertion product containing bridging oxo and aryl carbonate moieties, U(2)(OTtbp)(4)(μ-O)(μ-η(1):η(1)-O(2)COC(6)H(2)-Bu(t)(3)-2,4,6)(2), which has been structurally characterized. The presence of coordinated N(2) in [U(OTtbp)(3)](2)(N(2)) prevents the occurrence of any reaction with CO(2), underscoring the remarkable stability of the N(2) complex. The di-tert-butyl aryloxide does not insert CO(2), and only U(ODtbp)(4) was isolated. The silylamide also reacts with carbon dioxide to afford U(OSiMe(3))(4) as the only uranium-containing material. GGA and hybrid DFT calculations, in conjunction with topological analysis of the electron density, suggest that the U-N(2) bond is strongly polar, and that the only covalent U→N(2) interaction is π backbonding, leading to a formal (U(IV))(2)(N(2))(2-) description of the electronic structure. The N-N stretching wavenumber is preferred as a metric of N(2) reduction to the N-N bond length, as there is excellent agreement between theory and experiment for the former but poorer agreement for the latter due to X-ray crystallographic underestimation of r(N-N). Possible intermediates on the CO coupling pathway to [U(OAr)(3)](2)(μ-C(2)O(2)) are identified, and potential energy surface scans indicate that the ynediolate fragment is more weakly bound than the ancillary ligands, which may have implications in the development of low-temperature and pressure catalytic CO chemistry.

Covalency in CeIV and UIV Halide and N‐Heterocyclic Carbene Bonds

Oxidative halogenation with trityl chloride provides convenient access to Ce(IV) and U(IV) chloroamides [M(N{SiMe(3)}(2))(3)Cl] and their N-heterocyclic carbene derivatives, [M(L)(N{SiMe(3)}(2))(2)Cl] (L = OCMe(2)CH(2)(CNCH(2)CH(2)NDipp) Dipp = 2,6-iPr(2)C(6)H(3)). Computational analysis of the bonding in these and a fluoro analogue, [U(L)(N{SiMe(3)}(2))(2)F], provides new information on the covalency in this relative rare oxidation state for molecular cerium complexes. Computational studies reveal increased Mayer bond orders in the actinide carbene bond compared with the lanthanide carbene bond, and natural and atoms-in-molecules analyses suggest greater overall ionicity in the cerium complexes than in the uranium analogues.

Does covalency really increase across the 5f series? A comparison of molecular orbital, natural population, spin and electron density analyses of AnCp(3) (An = Th-Cm; Cp = eta(5)-C5H5)

The title compounds are studied with scalar relativistic, gradient-corrected (PBE) and hybrid (PBE0) density functional theory. The metal-Cp centroid distances shorten from ThCp(3) to NpCp(3), but lengthen again from PuCp(3) to CmCp(3). Examination of the valence molecular orbital structures reveals that the highest-lying Cp π(2,3)-based orbitals transform as 1e + 2e + 1a(1) + 1a(2). Above these levels come the predominantly metal-based 5f orbitals, which stabilise across the actinide series such that in CmCp(3) the 5f manifold is at more negative energy than the Cp π(2,3)-based levels. Mulliken population analysis shows metal d orbital participation in the e symmetry Cp π(2,3)-based orbitals. Metal 5f character is found in the 1a(1) and 1a(2) levels, and this contribution increases significantly from ThCp(3) to AmCp(3). This is in agreement with the metal spin densities, which are enhanced above their formal value in NpCp(3), PuCp(3) and especially AmCp(3) with both PBE and PBE0. However, atoms-in-molecules analysis of the electron densities indicates that the An-Cp bonding is very ionic, increasingly so as the actinide becomes heavier. It is concluded that the large metal orbital contributions to the Cp π(2,3)-based levels, and enhanced metal spin densities toward the middle of the actinide series arise from a coincidental energy match of metal and ligand orbitals, and do not reflect genuinely increased covalency (in the sense of appreciable overlap between metal and ligand levels and a build up of electron density in the region between the actinide and carbon nuclei).

Covalency in the f element-chalcogen bond. Computational studies of M N(EPR(2))(2) (3) (M = La, Ce, Pr, Pm, Eu, U, Np, Pu, Am, Cm; E = O, S, Se, Te; R = H, (i)Pr, Ph)

The geometric and electronic structures of the title complexes have been studied using scalar relativistic, gradient-corrected density functional theory. Extension of our previous work on six-coordinate M[N(EPH 2) 2] 3 (M = La, Ce, U, Pu; E = O, S, Se, Te), models for the experimentally characterized M[N(EP (i)Pr 2) 2] 3, yields converged geometries for all of the other 4f and 5f metals studied and for all four group 16 elements. By contrast, converged geometries for nine-coordinate M[N(EPPh 2) 2] 3 are obtained only for E = S and Se. Comparison of the electronic structures of six- and nine-coordinate M[N(EPH 2) 2] 3 suggests that coordination of the N atoms produces only minor changes in the metal-chalcogen interactions. Six-coordinate Eu[N(EPH 2) 2] 3 and Am[N(EPH 2) 2] 3 with the heavier group 16 donors display geometric and electronic properties rather different from those of the other members of the 4f and 5f series, in particular, longer than expected Eu-E and Am-E bond lengths, smaller reductions in charge difference between M and E down group 16, and larger f populations. The latter are interpreted not as evidence of f-based metal-ligand covalency but rather as being indicative of ionic metal centers closer to M (II) than M (III). The Cm complexes are found to be very ionic, with very metal-localized f orbitals and Cm (III) centers. The implications of the results for the separation of the minor actinides from nuclear wastes are discussed, as is the validity of using La (III)/U (III) comparisons as models for minor actinide/Eu systems.

Synthesis, Molecular and Electronic Structure of U-V(O) N(SiMe3)(2) (3)

Addition of 1 equiv of 2,2,6,6-tetramethylpiperidine-1-oxyl (TEMPO) to U(NR(2))(3) in hexanes affords U(O)(NR(2))(3) (2), which can be isolated in 73% yield. Complex 2 is a rare example of a terminal U(V) oxo complex. In contrast, addition of 1 equiv of Me(3)NO to U(NR(2))(3) (R = SiMe(3)) in pentane generates the U(IV) bridging oxo [(NR(2))(3)U](2)(μ-O) (3) in moderate yields. Also formed in this reaction, in low yield, is the U(IV) iodide complex U(I)(NR(2))(3) (4). The iodide ligand in 4 likely originates from residual NaI, present in the U(NR(2))(3) starting material. Complex 4 can be generated rationally by addition of 0.5 equiv of I(2) to a hexane solution of U(NR(2))(3), where it can be isolated in moderate yield as a tan crystalline solid. The solid-state molecular structures and magnetic susceptibilities of 2, 3, and 4 have been measured. In addition, the electronic structures of 2 and 3 have been investigated by density functional theory (DFT) methods.

Probing the reactivity and electronic structure of a uranium(V) terminal oxo complex

Treatment of the U(III)-ylide adduct U(CH(2)PPh(3))(NR(2))(3) (1, R = SiMe(3)) with TEMPO generates the U(V) oxo metallacycle [Ph(3)PCH(3)][U(O)(CH(2)SiMe(2)NSiMe(3))(NR(2))(2)] (2) via O-atom transfer, in good yield. Oxidation of 2 with 0.85 equiv of AgOTf affords the neutral U(VI) species U(O)(CH(2)SiMe(2)NSiMe(3))(NR(2))(2) (3). The electronic structures of 2 and 3 are investigated by DFT analysis. Additionally, the nucleophilicity of the oxo ligands in 2 and 3 toward Me(3)SiI is explored.

Does metallophilicity increase or decrease down group 11? Computational investigations of Cl-M-PH3 (2) ( M = Cu, Ag, Au, 111 )

The electronic and geometric structures of Cl–M–PH3 and [Cl–M–PH3]2 (M = Cu, Ag, Au, [111]) have been studied computationally using post Hartree–Fock ab initio and density functional methods. The trends in r(M–Cl) and r(M–P) in the monomers are discussed in the light of previous studies. Previous MP2 data on the metallophilic interactions in [Cl–M–PH3]2 (M = Cu, Ag, Au) are reproduced (to within basis set differences), and new MP2 data for the transactinide element 111 are presented. QCISD and coupled cluster calculations on the title systems are reported for the first time, and reveal that, contrary to the MP2 results, the strength of the metallophilic interaction essentially decreases as group 11 is descended.