Oxo Group Protonation and Silylation of Pentavalent Uranyl Pacman Complexes

Oxo group protonation and silylation of pentavalent uranyl Pacman complexes.

Easy access to stable pentavalent uranyl complexes.

Reaction of UO2I2(THF)3 with 1 molar equivalent of KC5R5 (R = H, Me) in pyridine led to the uranyl(V) compound {[UO2(Py)5][KI2(Py)2]}(infinity), which is an infinite 1D polymer in its crystalline form; the UO2X(THF)n (X = I, OSO2CF3) complexes were obtained by reduction of their U(VI) parents with TlC5H5 or KC5R5 in THF.

A macrocyclic approach to transition metal and uranyl Pacman complexes.

Multielectron redox chemistry involving small molecules such as O2, H2O, N2, CO2, and CH4 is intrinsic to the chemical challenges surrounding sustainable, low-carbon energy generation and exploitation. Compounds with more than one metal reaction site facilitate this chemistry by providing both unique binding environments and combined redox equivalents. However, controlling the aggregation of me...

The effect of the equatorial environment on oxo-group silylation of the uranyl dication: a computational study.

A theoretical investigation of the reductive oxo-group silylation reaction of the uranyl dication held in a Pacman macrocylic environment has been carried out. The effect of the modeling of the Pacman ligand on the reaction profiles is found to be important, with the dipotassiation of a single oxo group identified as a key component in promoting the reaction between the Si-X and uranium-oxo bon...

Equatorial ligand substitution by hydroxide in uranyl Pacman complexes of a Schiff-base pyrrole macrocycle.

The synthesis of the mono-uranyl complex [UO(2)(THF)(H(2)L(Me))] of a ditopic Schiff-base pyrrole macrocycle is described and is shown to adopt a Pacman wedge-shaped structure in which the uranyl dication is desymmetrised and sits solely in one N(4)-donor compartment to leave the other vacant. While investigating the mechanism of the previously reported, base-initiated, reductive silylation che...