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

Oxo group protonation and silylation of pentavalent uranyl Pacman complexes.

A Theoretical Study on Applying Conformational Analysis of 2-Halo-2-Oxo-1,3,2-Dioxaphosphorinanes

The quantum-chemical calculations on the conformational properties of 2-flouro-2-oxo- 1,3,2-dioxaphosphorinane (1), 2-choloro-2-oxo-1,3,2-dioxaphosphorinane (2) and 2-bromo- 2-oxo-1,3,2-dioxaphosphorinane (3) have been investigated by means of ab initio molecular orbital (HF/6-311+G**) and hybrid density functional theory (B3LYP/6-311+G**) based methods and Natural Bond Orbital (NBO) interpreta...

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...

Controlling uranyl oxo group interactions to group 14 elements using polypyrrolic Schiff-base macrocyclic ligands.

Heterodinuclear uranyl/group 14 complexes of the aryl- and anthracenyl-linked Schiff-base macrocyclic ligands LMe and LA were synthesised by reaction of UO2(H2L) with M{N(SiMe3)2}2 (M = Ge, Sn, Pb). For complexes of the anthracenyl-linked ligand (LA) the group 14 metal sits out of the N4-donor plane by up to 0.7 Å resulting in relatively short MOUO distances which decrease down the group; howev...

A STUDY OF THE SILYLATION REACTION OF IMINES WITH TRIMETHYLCHLOROSILANE IN THE PRESENCE OF LITHIUM

A mixture oftrimethylchlorosilane (TMS-Cl), lithium and tetrahydrofuran (THF) reacts with imines to produce disilyl compound by addition of two trimethylsilyl (TMS) groups to the double bond of the imine. On hydrolysis the TMS on nitrogen is substituted by hydrogen and yields ? -silylamine. In the presence of acetyl chloride (CH COC1), benzene and pyridine, the ?-silyamine produces the corresp...