Alistair S. P. Frey

Facile Conversion of CO/H2 into Methoxide at a Uranium(III) Center†

The reaction of [U(-C8H6{SiiPr3-1,4}2)(-Cp*)] in toluene with CO and H2 at sub to ambient temperature and pressure affords the methoxide complex [U(-C8H6{SiiPr3-1,4}2)(-Cp*)OMe]

UIII‐Induced Reductive Co‐Coupling of NO and CO to Form UIV Cyanate and Oxo Derivates

CO and NO give NCO and O! Sequential treatment of [U(?-C8H6{SiiPr3-1,4}2)(?-Cp*)] with CO followed by NO (or vice versa) affords a mixture of the bridging cyanate complex [{U(?-C8H6{SiiPr3-1,4}2)(?-Cp*)}2(µ-OCN)2] and the bridging oxo complex [{U(?-C8H6{SiiPr3-1,4}2)(?-Cp*)}2(µ-O)], both of which have been structurally characterised (see scheme).

Activation of P4 by U(η5-C5Me5)(η8-C8H6(SiiPr3)2-1,4)(THF); the X-ray structure of [U(η5-C5Me5)(η8-C8H6(SiiPr3)2-1,4)]2(μ-η2:η2-P4)

The uranium(III) mixed sandwich complex [U(η5-C5Me5)(η8-C8H6(SiiPr3)2-1,4)(THF)] reacts with white phosphorus to afford dimeric [U(η5-C5Me4H)(η8-C8H6(SiiPr3)2-1,4)]2(μ-η2:η2−P4), whose X-ray structure reveals a novel η2,η2bonding mode for the bridging P4 unit. DFT computational studies confirm that the P4 ring is doubly reduced and show interaction of the uranium atoms with both a σ and a π orbital of the P4 ring.

Reductive disproportionation of carbon dioxide by a sm(II) complex: unprecedented f-block element reactivity giving a carbonate complex.

A macrocyclic organosamarium(II) complex has been shown to provide the first example of the reductive disproportionation of carbon dioxide, giving a bimetallic carbonate complex and carbon monoxide in a facile reaction under ambient conditions.