Oxo group protonation and silylation of pentavalent uranyl Pacman complexes.
نویسندگان
چکیده
منابع مشابه
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...
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Reactions between the uranyl(VI) Pacman complex [(UO2)(py)(H2L)] of the Schiff-base polypyrrolic macrocycle L and Tebbe's reagent or DIBAL result in the first selective reductive functionalisation of the uranyl oxo by Al to form [(py)(R2AlOUO)(py)(H2L)] (R = Me or (i)Bu). The clean displacement of the oxo-coordinated Al(III) by Group 1 cations has enabled the development of a one-pot, DIBAL-cat...
متن کاملEquatorial 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...
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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...
متن کاملControlling 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...
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ورودعنوان ژورنال:
- Angewandte Chemie
دوره 50 40 شماره
صفحات -
تاریخ انتشار 2011