ALDRIDGE GROUP

GROUP 13 LIGANDS

Sequential BH activation (MO)

Group 13 radicals (AP)

D-block boryls/bora-acyls (RF)

Bora-Neigichi chemistry (JC)

(Recent work by Mike ONeill, Andrey Protchenko, Rene Frank and Jesus Campos)

The activation of boranes by a metal complex is a key step in a number of important catalytic reactions, including hydroboration, functionalization of unactivated C-H bonds and dehydrocoupling of amineboranes. The coordination of BH bonds at Transition Metal centres, and their subsequent activation to give boryl and borylene systems is therefore of critical importance. In the Aldridge group we have an ongoing interest in complexes of these types, together with their heavier Group 13 analogues. Current projects include:

Sigma complexes of B-H, Al-H and Ga-H bonds. We are engaged in systematic studies of the fundamental modes of interaction of boranes with 14- and 16-electron metal centres, and the manner in which such systems can be undergo further B-H activation. Recently we have been examining the possibility for similar activation processes with Al-H and Ga-H bonds.

Metal boryl complexes. The formally anionic boryl ligand (BX2-) is about the strongest sigma donor ligand currently available. We have been developing new routes to metal boryl complexes, with a view to exploiting the unique electronic properties of these ligands to develop new patterns of metal-centred reactivity. These include novel complexes of p-, d-, and f-block metals, and systems capable of hitherto unprecedented bond activation processes.

Complexes containing the borylene ligand (BX) and heavier Group 13 analogues are of fundamental interest, being isoelectronic with the near ubiquitous organometallic ligand CO.

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Copyright S Aldridge

2016

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