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     New Chemistry

 

 

 

     A transition metal borylene

     complex stabilized by a non-

     carbonyl ligand set: formation

     by spontaneous halide loss to

     give an extremely short metal-

     -boron bond (video).

     (work by David Addy)

 

 

 

Aldridge


Transition Metal Boryl and Related Complexes

 

Transition metal boryl complexes (LnMBX2) are highly topical compounds, due to their implication in an number of versatile organic transformations including metal-catalysed hydro- and diboration, and most notably, the catalytic functionalization of C-H bonds in arenes and alkanes - one of the ‘Holy Grails’ of organometallic chemistry. Thus, catalytic systems involving boryl complexes as intermediates, will selectively react at the terminal C-H bonds of alkanes such as octane to give useful organic products containing C-B bonds.

 

We have been involved in this area principally with the aim of better understanding the fundamental issues of electronic structure which underpin this unusual reactivity. Thus, novel synthetic, spectroscopic and computational approaches have been used to investigate the role of the formally vacant boron-centred p-orbital in structural and reaction chemistry. Recent work has revealed an alternative mechanism for attack at C-H bonds by perfluoroaryl metal boryl systems.

 

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A related project is concerned with the activation of B-H and N-H bonds by transition metal complexes, and specifically with the elucidation of fundamental steps in the dehydrogenative coupling of amine boranes BH3.NRnH3-n. Such processes are of potential importance in hydrogen storage applications, and a number of novel iridium systems synthesized as part of a new EPSRC-funded project have shown promising initial results in this area.

 

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     Further Information

 

 

 

     Research Areas Overview

         Multiply bonded systems

         Metal boryl complexes

         Sensors

         Sterically demanding ligands

         References

         Collaborations

         Current project funding

 

 

 

     Figures

 

 

 

     (top) Insertion of a boryl ligand

     fragment into a C-H bond of an

     ancillary cyclopentadienyl ligand

     in the presence of CO. See:

     Chem. Commun. 2006, 2578.

 

     (bottom, l to r) Ribbon-like motif of

     solid methylamine borane, featuring

     unconventional N-H to H-B hydrogen

     bonds; crystal structure of a doubly

     C-H activated Ir carbene complex

     which shows interesting reactivity

     towards amine-boranes.

     See: EPSRC ‘green chemistry’ grant.

 

 

     New chemistry (video)

 

 

 

     Benzyl C-H functionalization by boro-

     hydride – one of intermediates iso-

     lated on reaction path. Click here.

     (work of Dr Christina Tang)