PhD Project - PhD Studentship in C–H Functionalisation Using Polymetallic Complexes at Imperial College London, listed on FindAPhD.com

The heavier, the better! We report that the caesium congener is the most active and versatile catalyst amongst a full group set of well-defined crown ether supported alkali metal diphenyl phosphides ...

Previous studies have hinted at the similarities of Mn(II) and Mg alkyl complexes. Advancing this field, here we present a comparative study of tetra(n-butyl) lithium manganate(II) and magnesiate. Com...

Low-valent cadmium compounds have remained largely unexplored as electron reservoirs, with no precedent for their use in reduction or bond activation chemistry. Here, we address this gap by integratin...

The potassium aluminyl K[Al(NON)] reacts with Ge[N(SiMe3)2]2 by a sequential reductive deamination pathway. The initially formed aluminacyclodigermene contains Ge(I) centres and may be considered as ...

The β-diketiminato calcium hydride, [(BDI)CaH]2 (BDI = HC{(Me)CNDipp}2, where Dipp = 2,6-i-Pr2C6H3), reacts with [Zn{N(SiMe3)2}2] and [Zn(TMP)2] (TMP = 2,2,6,6-tetramethylpiperidide) to provide labile...

The reaction of a dihydro-dialane supported by a hybrid ligand (DNI) with organic azides yields structurally diverse aluminium species, including the first example of low oxidation state aluminium az...

The author had been using research “as a way of trying to control the uncontrollable”

A free-flowing, homogeneous and non-pyrophoric powder of Na/NaCl is prepared via planetary ball-milling. The mechanochemically micronised Na/NaCl serves as a highly activated source of sodium and was ...

Promoting societally important small molecule activation processes with earth-abundant metals is foundational for a sustainable chemistry future. In this context, mapping new reaction pathways that would enable abundant main-group elements to mimic the behaviors of d- and f-block elements is facilitated by exploring unusual oxidation states. The most abundant metal on earth, aluminum, has been well studied in the Lewis acidic +III and Lewis basic +I oxidation states but rarely in the potentially biphilic +II oxidation state until recently, when a renaissance of Al(II) chemistry emerged from a range of research groups. In this Perspective, we review the chemistry of mononuclear Al radicals, including both Al-centered radicals (i.e., Al(II) compounds) and redox non-innocent systems (i.e., formally Al(II) species that are physically Al(III) with ligand-centered radicals), with an emphasis on small molecule reactivity. We also provide a meta-analysis of the Al(II) literature to summarize how different design strategies (e.g., redox non-innocence, strained coordination geometries) have been shown to impart biphilic character to Al radicals and tune their behavior, thus allowing Al radicals to mimic the chemistry of certain d- and f-block metal ions such as Ti(III) and Sm(II). We expect these molecular design concepts to inform future Al(II) studies as the chemistry of this unusual oxidation state of Al continues to grow.

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