In-Plane Thorium(IV), Uranium(IV), and Neptunium(IV) Expanded Porphyrin Complexes.

Here we report the first series of in-plane thorium(IV), uranium(IV), and neptunium(IV) expanded porphyrin complexes. These actinide (An) complexes were synthesized using a hexa-aza porphyrin analogue, termed dipyriamethyrin, and the nonaqueous An(IV) precursors, ThCl(DME), UCl, and NpCl(DME). The molecular and electronic structures of the ligand, each An(IV) complex, and a corresponding uranyl(VI) complex were characterized using nuclear magnetic resonance (NMR) and UV-vis spectroscopies as well as single-crystal X-ray diffraction analysis.

Isolation of a TMTAA-Based Radical in Uranium bis-TMTAA Complexes.

We report the synthesis, characterization, and electronic structure studies of a series of thorium(IV) and uranium(IV) bis-tetramethyltetraazaannulene complexes. These sandwich complexes show remarkable stability towards air and moisture, even at elevated temperatures. Electrochemical studies show the uranium complex to be stable in three different oxidation states; isolation of the oxidized species reveals a rare case of a non-innocent tetramethyltetraazaannulene (TMTAA) ligand.

New supporting ligands in actinide chemistry: tetramethyltetraazaannulene complexes with thorium and uranium.

We report the synthesis, characterization, and preliminary reactivity of new heteroleptic thorium and uranium complexes supported by the macrocyclic TMTAA ligand (TMTAA = Tetramethyl-tetra-aza-annulene). The dihalide complexes Th(TMTAA)Cl(THF) (1), [UCl(TMTAA)] (2) and U(TMTAA)I (3) are further functionalized to the Cp* derivatives ThCp*(TMTAA)Cl (4), UCp*(TMTAA)Cl (5) and UCp*(TMTAA)I (6) (Cp* = pentamethylcyclopentadienide). Compounds 4-6 are also obtained through a one-pot reaction from standard thorium(iv) and uranium(iv) starting materials, Li2TMTAA and KCp*.

Thorium Metallacycle Facilitates Catalytic Alkyne Hydrophosphination.

The bis(NHC)borate-supported thorium-bis(mesitylphosphido) complex (1) undergoes reversible intramolecular C-H bond activation enabling the catalytic hydrophosphination of unactivated internal alkynes. Catalytic and stoichiometric experiments support a mechanism involving reactive Th-NHC metallacycle intermediates (Int and 2).

Benzoquinonoid-bridged dinuclear actinide complexes.

We report the coordination chemistry of the tripodal tris[2-amido(2-pyridyl)ethyl]amine ligand, L, with thorium(iv) and uranium(iv). Using a salt-metathesis strategy from the potassium salt of this ligand, K3L, new actinide complexes were isolated, namely the dimeric thorium complex [ThCl(L)] (1) and the monomeric uranium complex UI(THF)(L) (2); under different crystallisation conditions, the dimeric uranium complex is also isolated, [UI(L)] (2-dimer). With the aim of studying electronic phenomena such as magnetic exchange between two actinide ions, we have synthesised the first examples of dinuclear, quinoid-bridged actinide complexes from dianionic 2,5-bis[2,6-(diisopropyl)anilide]-1,4-benzoquinone (QDipp) and 2,5-bis[2-(methoxy)anilide]-1,4-benzoquinone (QOMe) ligands.

A Thorium Chalcogenolate Series Generated by Atom Insertion into Thorium-Carbon Bonds.

A new thorium monoalkyl complex, Th(CHSiMe)(L) (L = MeC(NPr)) (2), undergoes insertion of chalcogen atoms resulting in a series of thorium chalcogenolate complexes, Th(ECHSiMe)(L) (E = S, SS, Se, Te; 5-8). Complex 6 represents the first alkyl disulfide thorium species and illustrates the ability of 2 to undergo controllable, stoichiometric atom insertion. All complexes have been characterized by H and C NMR spectroscopy, FTIR, EA, and melting point, and in the case of 1, 2, and 4-8, X-ray crystallography.

Carbon-Nitrogen Bond Cleavage by a Thorium-NHC-bpy Complex.

Actinide complexes demonstrate unparalleled reactivity towards small molecules. However, utilizing these powerful transformations in a predictable and deliberate manner remains challenging. Therefore, developing actinide systems that not only perform noteworthy chemistry but also demonstrate controllable reactivity is a key goal.

N-heterocyclic carbene gold(I) and silver(I) complexes bearing functional groups for bio-conjugation.

This work describes several synthetic approaches to append organic functional groups to gold and silver N-heterocyclic carbene (NHC) complexes suitable for applications in biomolecule conjugation. Carboxylate appended NHC ligands (3) lead to unstable Au(I) complexes that convert into bis-NHC species (4). A benzyl protected carboxylate NHC-Au(I) complex 2 was synthesized but deprotection to produce the carboxylic acid functionality could not be achieved.